TW202110954A - Negative type curable composition, cured film, layered body, cured film production method, and semiconductor device - Google Patents

Abstract

The invention provides: a negative type curable composition comprising an alkali-soluble polyimide, a photopolymerization initiator, and a bifunctional cross-linking agent having no covalent cyclic structure other than the polymerization groups, the polymerization groups being distanced from one another by 12 or more atoms; a cured film yielded by curing the negative type curable composition; a layered body containing the cured film; a production method for the cured film; and a semiconductor device containing the cured film or the layered body.

Description

Negative curable composition, cured film, laminate, cured film manufacturing method and semiconductor device

The present invention relates to a method for manufacturing a negative curable composition, a cured film, a laminate, a cured film, and a semiconductor device.

Polyimide resin is excellent in heat resistance and insulation, so it can be applied to various applications. The use is not particularly limited, but if a semiconductor device for actual mounting is taken as an example, the use as a material for an insulating film or a sealing material or a protective film can be cited. It is also used as a base film or cover film for flexible substrates.

For example, in the above application, the polyimide resin is used in the form of a negative curable composition containing an alkali-soluble polyimide resin. For example, the negative-type curable composition is applied to a substrate by coating or the like, and then exposed, developed, heated, etc. as necessary, whereby a hardened resin can be formed on the substrate. The negative-type curable composition can be applied by a well-known coating method. Therefore, it can be said that, for example, the shape, size, and application position of the applied negative-type curable composition have a high degree of freedom in design and excellent manufacturing adaptability. . In addition to the high performance of polyimide, etc., it is also excellent in manufacturing adaptability, and there is an increasing expectation for the industrial application of negative curable compositions containing alkali-soluble polyimide. expand.

For example, Patent Document 1 describes a photosensitive resin composition characterized by containing alkali-soluble polyimide (a), unsaturated bond-containing compound (b), thermally crosslinkable compound (c) and having a specific Structured photopolymerization initiator (d).

[Patent Document 1] International Publication No. 2018/173840

In the negative-type curable composition containing alkali-soluble polyimide, it is desired to provide a negative-type curable composition having excellent elongation at break of the obtained cured product.

The object of the present invention is to provide a negative-type curable composition having excellent elongation at break of the obtained cured film, a cured film formed by curing the negative-type curable composition, a laminate including the cured film, and the The manufacturing method of a cured film, and the semiconductor device containing the said cured film or the said laminated body.

Hereinafter, examples of representative embodiments of the present invention are shown. <1> A negative type hardening composition, which contains: Alkali-soluble polyimide; Photopolymerization initiator and The bifunctional crosslinking agent does not have a cyclic structure based on a covalent bond at a site other than the polymerized group, and the distance between the polymerized groups is 12 atoms or more. <2> The negative curable composition according to <1>, wherein the bifunctional crosslinking agent contains a polyoxyalkylene group. <3> The negative curable composition according to <1> or <2>, wherein the bifunctional crosslinking agent includes a compound that causes a polymerization reaction by the photosensitivity of the photopolymerization initiator. <4> The negative curable composition according to any one of <1> to <3>, wherein the bifunctional crosslinking agent includes a thermal crosslinking agent. <5> The negative-type curable composition according to any one of <1> to <4>, wherein the alkali-soluble polyimide has a fluorine atom. <6> The negative-type curable composition according to any one of <1> to <5>, wherein the alkali-soluble polyimide has a silicon atom. <7> The negative curable composition according to any one of <1> to <6>, wherein the alkali-soluble polyimide has an ethylenically unsaturated bond. <8> The negative-type curable composition according to any one of <1> to <7>, wherein the alkali-soluble polyimide has a phenolic hydroxyl group. <9> The negative curable composition according to any one of <1> to <8>, which further comprises a compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure At least one compound. <10> The negative curable composition according to any one of <1> to <9>, wherein the photopolymerization initiator is an oxime compound. <11> The negative curable composition according to any one of <1> to <10>, which further comprises at least one selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent Compound. <12> The negative curable composition according to any one of <1> to <11>, which further contains a compound having 3 to 6 ethylenically unsaturated bonds. <13> The negative-type curable composition according to any one of <1> to <12>, which is used for forming an interlayer insulating film for a rewiring layer. <14> A cured film formed by curing the negative-type curable composition described in any one of <1> to <13>. <15> A laminate comprising two or more layers of the cured film described in <14>, and a metal layer between any of the cured films. <16> A method for producing a cured film, which includes a film forming process of applying the negative curable composition described in any one of <1> to <13> to a substrate to form a film. <17> The method for producing a cured film as described in <16>, which includes an exposure process for exposing the film and a development process for developing the film. <18> The method for producing a cured film as described in <16> or <17>, which includes a heating process of heating the film at 50 to 450°C. <19> A semiconductor device comprising the cured film described in <14> or the laminated body described in <15>. [Effects of the invention]

According to the present invention, there is provided a negative-type curable composition having excellent elongation at break of the obtained cured film, a cured film formed by curing the negative-type curable composition, a laminate including the cured film, and the cured film A method of manufacturing a film and a semiconductor device including the above-mentioned cured film or the above-mentioned laminate.

Hereinafter, the main embodiment of the benzene invention will be described. However, the present invention is not limited to the illustrated embodiment. In this specification, the numerical range indicated by the symbol "～" means the range that includes the numerical values described before and after the "～" as the lower limit and the upper limit, respectively. In this specification, the term "process" not only refers to an independent process, but as long as it can achieve the required effect of the process, it also means a process that cannot be clearly distinguished from other processes. Regarding the label of the group (atomic group) in this specification, the label not labeling substituted and unsubstituted includes both a group without a substituent (atomic group) and a group with a substituent (atomic group). For example, "alkyl" includes not only unsubstituted alkyl (unsubstituted alkyl) but also substituted alkyl (substituted alkyl). In this specification, "exposure" is not particularly limited, and includes exposure with particle beams such as electron beams and ion beams in addition to exposure with light. In addition, as the light used for exposure, actinic rays or radiations such as the bright line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams can be cited. In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic" and "methacrylic" For both or either of them, "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of the components except the solvent from the total components of the composition. In addition, in this specification, the solid content concentration is the mass percentage of components other than the solvent with respect to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are based on gel permeation chromatography (GPC measurement), and are defined as polystyrene conversion values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220GPC (manufactured by TOSOH CO Ar PORATION), and protection columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000 can be used , TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) are calculated as the column. Unless otherwise specified, these molecular weights will be measured using THF (tetrahydrofuran) as the eluent. In addition, unless otherwise specified, the detection in the GPC measurement uses a UV ray (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting the layered body is described as "upper" or "lower", it is only necessary that another layer exists on the upper side or the lower side of the reference layer among the plurality of layers of interest. That is, the third layer or the third element may be further sandwiched between the layer serving as the reference and the other layer described above, and the layer serving as the reference does not need to be in contact with the other layer described above. In addition, unless otherwise specified, the direction of the stacked layers of the base material is referred to as "up", or when the photosensitive layer is present, the direction from the base material to the photosensitive layer is referred to as "up", and the opposite direction is referred to as "up". under". In addition, the setting of this vertical direction is for the convenience of this specification. In an actual aspect, the "up" direction in this specification may also be different from the vertical up direction. In this specification, as long as there is no special description, as each component contained in the composition, the composition may contain two or more compounds that conform to the component. In addition, unless otherwise stated, the content of each component in the composition indicates the total content of all the compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C and the air pressure is 101,325 Pa (1 atmosphere). In this specification, a combination of preferred aspects is a more optimal aspect.

(Negative hardening composition) The negative-type curable composition of the present invention contains alkali-soluble polyimide, a photopolymerization initiator, and does not have a cyclic structure based on covalent bonds at positions other than polymerized groups, and the distance between the polymerized groups is 12 A bifunctional crosslinking agent with more than one atom (hereinafter, also referred to as "specific bifunctional crosslinking agent"). The negative-type curable composition of the present invention preferably further includes at least one compound selected from the group consisting of the compound having a sulfonamide structure described later and the compound having a thiourea structure described later. The negative curable composition of the present invention preferably further contains at least one compound selected from the group consisting of the urea-based crosslinking agent described below and the melamine-based crosslinking agent described below. The negative curable composition of the present invention preferably further contains a compound having 3 to 6 ethylenically unsaturated bonds. In addition, the negative-type curable composition of the present invention is a composition in which the non-exposed area is removed by development when the development is performed after exposure.

Regarding the negative-type curable composition of the present invention, the cured film obtained from the above composition is excellent in elongation at break. The mechanism for obtaining the above effects is not clear, but it can be presumed as follows.

The negative-type curable composition is used for applications such as obtaining a cured film by heating or the like after being applied to a substrate or the like. In addition, if necessary, for example, patterning can be performed by exposure and development before heating. Among them, in the currently used cured film formed using a negative curable composition containing alkali-soluble polyimide, there is still room for further improvement in the elongation at break of the cured film. Therefore, the inventors of the present invention conducted intensive studies and found that by cross-linking bifunctional groups that do not have a cyclic structure based on covalent bonds at positions other than the polymerized group and the distance between the polymerized groups is 12 atoms or more The agent is used as a cross-linking agent, and the elongation at break of the cured film is improved. The reason for obtaining the above effect is not clear, but it is presumed as follows: The above-mentioned bifunctional crosslinking agent does not have a cyclic structure based on a covalent bond at a site other than the polymerized group, and the distance between the polymerized groups is 12 atoms or more, Therefore, the hardened structure becomes a relatively flexible structure, thereby increasing the elongation at break of the cured film.

Among them, in Patent Document 1, there is neither description nor suggestion regarding the improvement of the elongation at break of the cured film by using a bifunctional crosslinking agent whose distance between the polymer groups is 12 atoms or more. Hereinafter, the components contained in the negative curable composition of the present invention will be described in detail.

＜Alkali-soluble polyimide＞ The negative-type curable composition of the present invention contains alkali-soluble polyimide. In this specification, alkali-soluble polyimide means that 0.1 g or more of polyimide is dissolved in 100 g of 2.38% by mass tetramethylammonium aqueous solution at 23°C. From the viewpoint of pattern formation, 0.5 g is dissolved The above polyimine is preferable, and it is more preferable to dissolve 1.0 g or more of polyimine. The upper limit of the above-mentioned dissolution amount is not particularly limited, but 100 g or less is preferable. Moreover, regarding alkali-soluble polyimide, from the viewpoint of the elongation at break and insulating properties of the cured film obtained, a polyimide having a plurality of imine structures in the main chain is preferred. In this specification, the "main chain" means the relatively longest bonding chain in the molecule of the polymer compound constituting the resin, and the "side chain" means the other bonding chain.

[Fluorine atom] From the viewpoint of the elongation at break of the cured film obtained, it is preferable that the alkali-soluble polyimide has a fluorine atom. The fluorine atom is contained in, for example, R ^{115 in the structure represented by formula (1-1) mentioned later, R 132} in the repeating unit represented by formula (2-1) mentioned later, or represented by formula (2-1) mentioned later ^{R 131} in the repeating unit is preferable, and the fluorinated alkyl group includes R ^{115 in} the structure represented by the formula (1-1) described later, and the repeating unit represented by the formula (2-1) described later R ^{132 or R 131} in the repeating unit represented by formula (2-1) described later is more preferred. The amount of fluorine atoms relative to the total mass of the alkali-soluble polyimide is preferably 1-50 mol/g, more preferably 5-30 mol/g.

[Silicon atom] From the viewpoint of the elongation at break of the cured film obtained, it is preferable that the alkali-soluble polyimide has a silicon atom. Silicon atoms contained in the later-described example of the repeating unit represented by the formula (2-1) is preferred in the R ¹³¹ as described later, the modified organic (poly) siloxane structure comprising silicon after the described by the formula (2-1) ^{R 131} in the repeating unit shown is more preferable. In addition, the silicon atom or the organic modified (poly)siloxane structure may be included in the side chain of the alkali-soluble polyimide, but it is preferably included in the main chain of the alkali-soluble polyimide. The amount of silicon atoms relative to the total mass of the alkali-soluble polyimide is preferably 0.01-5 mol/g, more preferably 0.05-1 mol/g.

[Ethylene Unsaturated Bond] From the viewpoint of the elongation at break of the cured film to be obtained, it is preferable that the alkali-soluble polyimide has an ethylenically unsaturated bond. The alkali-soluble polyimide may have an ethylenically unsaturated bond at the end of the main chain, or may have an ethylenic unsaturated bond in the side chain, and preferably has an ethylenically unsaturated bond in the side chain. It is preferable that the above-mentioned ethylenically unsaturated bond has radical polymerizability. ^{The ethylenically unsaturated bond is contained in R 115 in} the structure represented by the formula (1-1) mentioned ^{later, R 132} in the repeating unit represented by the formula (2-1) mentioned later, or by the formula (2-1) mentioned later ^{R 131} in the repeating unit represented by) is preferably included as a group having an ethylenically unsaturated bond in the structure represented by formula (1-1) ^{described later, R 115 in} the structure represented by formula (1-1) described later, and formula (2-1) described later ^{R 132} in the repeating unit represented by) ^{or R 131} in the repeating unit represented by formula (2-1) described later is more preferred. Among these, it is preferable that the ethylenically unsaturated bond is contained in the repeating unit represented by the formula (2-1) described later in R ¹³¹ , and the group having the ethylenically unsaturated bond is contained in the following formula ( ^{2-1) R 131} in the repeating unit indicated is more preferred. Examples of groups having ethylenically unsaturated bonds include groups such as vinyl groups, allyl groups, and vinyl phenyl groups that have a vinyl group that may be directly bonded to an aromatic ring, and (meth)acrylic acid groups. An amino group, a (meth)acryloxy group, a group represented by the following formula (III), and the like.

[Chemical formula 1]

In the formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred.

In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH -. (Poly)oxyalkylenes with 2-30 carbons (the carbon number of the alkylenes is preferably 2-12, more preferably 2-6, particularly preferably 2 or 3; repeating number is 1-12 Is preferred, 1 to 6 are more preferred, and 1 to 3 are particularly preferred) or a combination of two or more groups. In addition, (poly)oxyalkylene means oxyalkylene or polyoxyalkylene.

在式（R1）～（R3）中，L表示單鍵或碳數2～12的伸烷基、碳數2～30的（聚）氧伸烷基或將該等鍵結2個以上之基團，X表示氧原子或硫原子，*表示與其他結構的鍵結部位，●表示與式（III）中的R²⁰¹ 所鍵結之氧原子的鍵結部位。 在式（R1）～（R3）中，L中的碳數2～12的伸烷基或碳數2～30的（聚）氧伸烷基的較佳態樣與上述R²⁰¹ 中的碳數2～12的伸烷基或碳數2～30的（聚）氧伸烷基的較佳態樣相同。 在式（R1）中，X係氧原子為較佳。 在式（R1）～（R3）中，*的含義與式（III）中的*相同，較佳態樣亦相同。 由式（R1）表示之結構例如可藉由使酚性羥基等具有羥基之聚醯亞胺與具有異氰酸基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-異氰酸基乙酯等）進行反應來獲得。 由式（R2）表示之結構例如可藉由使具有羧基之聚醯亞胺與具有羥基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-羥基乙酯等）進行反應來獲得。 由式（R3）表示之結構例如可藉由使酚性羥基等具有羥基之聚醯亞胺與具有環氧丙基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸環氧丙酯等）進行反應來獲得。Among these, R ²⁰¹ is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1). [Chemical formula 2]

In the formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbons, a (poly)oxyalkylene group having 2 to 30 carbons, or a group bonding these two or more X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bonding site with an oxygen atom bonded to ^{R 201 in formula (III).} In the formulas (R1) to (R3), the preferred aspect of the alkylene having 2 to 12 carbons or the (poly)oxyalkylene having 2 to 30 carbons in L is the same as the number of carbons in the ^{above R 201} The preferred aspects of the 2-12 alkylene group or the (poly)oxyalkylene group having 2-30 carbon atoms are the same. In the formula (R1), the X-based oxygen atom is preferred. In formulas (R1) to (R3), * has the same meaning as * in formula (III), and preferred aspects are also the same. The structure represented by the formula (R1) can be obtained, for example, by making a polyimide having a hydroxyl group such as a phenolic hydroxyl group and a compound having an isocyanate group and an ethylenically unsaturated bond (for example, methacrylic acid 2-isocyanate group) Ethyl ester, etc.) to be obtained by reaction. The structure represented by the formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.). The structure represented by the formula (R3) can be formed by, for example, polyimide having a hydroxyl group such as a phenolic hydroxyl group and a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.) It is obtained by reaction.

In the formula (III), * represents the bonding site with other structures, and the bonding site with the main chain of the polyimide is preferred.

The amount of ethylenically unsaturated bonds relative to the total mass of the alkali-soluble polyimide is preferably 0.05-10 mol/g, more preferably 0.1-5 mol/g.

[Crosslinkable group other than ethylenically unsaturated bond] The alkali-soluble polyimide may have a crosslinkable group other than the ethylenically unsaturated bond. Examples of crosslinkable groups other than ethylenically unsaturated bonds include cyclic ether groups such as epoxy groups and oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups. R crosslinkable groups other than an ethylenically unsaturated bond, for example, contained in the repeating unit represented by the sum of the later-described formula (2-1) ¹³¹ is preferred. The amount of crosslinkable groups other than the ethylenically unsaturated bond relative to the total mass of the alkali-soluble polyimide is preferably 0.05-10 mol/g, more preferably 0.1-5 mol/g.

〔Acid value〕 From the viewpoint of improving developability, the acid value of the alkali-soluble polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more. In addition, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. The above-mentioned acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. In addition, as the acid group contained in the alkali-soluble polyimide, from the viewpoint of both storage stability and developability, an acid group having a pKa of 0 to 10 is preferred, and an acid group of 3 to 8 is more preferred. pKa considers the dissociation reaction of hydrogen ions released from oxygen and expresses its equilibrium constant Ka by its negative common logarithm pKa. In this specification, unless otherwise specified, pKa is set to a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, you can refer to the values described in the "Revised 5th Edition Chemistry Handbook Basics" compiled by the Chemical Society of Japan. In addition, when the acid group is a polybasic acid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant. As the acid group, the alkali-soluble polyimide preferably contains at least one selected from the group including a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[Phenolic hydroxyl group] From the viewpoint of making the development speed based on an alkali developer appropriate, it is preferable that the alkali-soluble polyimide has a phenolic hydroxyl group. The alkali-soluble polyimide may have a phenolic hydroxyl group at the end of the main chain, or may have a phenolic hydroxyl group at the side chain. The phenolic hydroxyl group is contained in, for example, R ^{115 in the structure represented by formula (1-1) mentioned later, R 132} in the repeating unit represented by formula (2-1) mentioned later, or formula (2-1) mentioned later ^{R 131} in the repeating unit shown is preferred. The amount of the phenolic hydroxyl group relative to the total mass of the alkali-soluble polyimide is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g.

在式（1-1）中，R¹¹⁵ 表示4價有機基團。[Structure represented by formula (1-1)] Furthermore, it is preferable that the alkali-soluble polyimide has a structure represented by the following formula (1-1), and has a structure represented by the following formula (1-1) in the main chain The structure shown is better. [Chemical formula 3]

In formula (1-1), R ¹¹⁵ represents a tetravalent organic group.

-R ¹¹⁵ -In the above formula (1-1), R ¹¹⁵ is preferably a tetravalent organic group containing an aromatic ring, a group represented by the following formula (1-2) or formula (1-3) For better.

[Chemical formula 4]

In formula (1-2), R ¹¹² is a divalent linking group, a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that can be substituted with a fluorine atom, -O-, -C(=O)-, -S -, -S(=O) ₂ -, -NHC(=O)- or a combination of 2 or more groups is preferred, single bond or selected from carbon number 1 to 3 which can be substituted by fluorine atom Groups among alkylene, -O-, -C(=O)-, -S- and S(=O) ₂ -are more preferably selected from the group including -CH ₂ -, -O-, -S- The divalent group in the group of -S(=O) ₂ -, -C(CF ₃ ) ₂ -and -C(CH ₃ ) _{2-is further preferred.} * Each independently indicates the bonding site with other structures.

^{Regarding the tetravalent organic group represented by R 115} in the formula (1-1), specifically, the tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride and the like can be mentioned. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. Tetracarboxylic dianhydride is preferably a compound represented by the following formula (1-4).

[Chemical formula 5]

In formula (1-4), R ¹¹⁵ represents a tetravalent organic group. The same meaning as R ¹¹⁵ R ¹¹⁵ in the formula (1-1), preferred aspects are also the same.

As a specific example of tetracarboxylic dianhydride, can be exemplified selected from pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3 ',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethyl Ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3 ,3',4'-Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2 ,3,6,7-Naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2, 2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3 ,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4 ,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10- Phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2 ,3,4-Benzenetetracarboxylic dianhydride and at least one of these alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Moreover, as a preferable example, the tetracarboxylic dianhydride (DAA-1)-(DAA-5) shown below can also be mentioned.

[Chemical formula 6]

在式（2-1）中，R¹³¹ 表示2價有機基團，R¹³² 表示4價有機基團。[Repeating unit represented by the formula (2-1)] Furthermore, it is preferable that the alkali-soluble polyimide has a repeating unit represented by the following formula (2-1), and the main chain has a repeating unit represented by the following formula (2- 1) The repeating unit indicated is preferred. [Chemical formula 7]

In formula (2-1), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.

在式（SI-1）中，R^S 分別獨立地表示氫原子或有機基團，R^S 中的至少1個表示有機基團，n表示1以上的整數，*分別獨立地表示與其他結構的鍵結部位。-R ¹³¹ -In the formula (2-1), ^{examples of the divalent organic group represented by R 131 include} linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups , Organically modified (poly)siloxane structure or a combination of two or more groups, straight-chain aliphatic groups with 2-20 carbons, branched aliphatic groups with 3-20 carbons, carbon A cyclic aliphatic group with 3-20, an aromatic hydrocarbon group with 6-20 carbons, an organically modified (poly)siloxane structure, or a combination of two or more groups of these are preferred, with 6 carbons The aromatic hydrocarbon group of -20 is more preferable. The linear or branched aliphatic group, the cyclic aliphatic group or the aromatic group may have a substituent. Examples of the substituent include an alkyl group, a hydroxyl group, a thiol group, a carboxyl group, and the above Groups having ethylenically unsaturated bonds, crosslinkable groups other than the above-mentioned ethylenically unsaturated bonds, etc. The above-mentioned organically modified (poly)siloxane structure includes both an organically modified siloxane structure containing only one siloxane structure and an organically modified polysiloxane structure containing two or more siloxane structures . As the above-mentioned organically modified (poly)siloxane structure, a structure represented by the following formula (SI-1) is preferred. [Chemical formula 8]

In the formula (SI-1), R ^S each independently represents a hydrogen atom or an organic group, ^{at least one of R S} represents an organic group, n represents an integer of 1 or more, and * each independently represents a relationship with other structures. Bonding site.

In formula (SI-1), R ^S each independently represents a hydrogen atom, an alkyl group or an aryl group, preferably, an alkyl group having 1 to 10 carbons or an aryl group having 6 to 20 carbons. The alkyl group or phenyl group of 1 to 4 is more preferable, the methyl group or the phenyl group is particularly preferable, and the methyl group is most preferable. In addition, ^{at least one of R S} represents an organic group, and it is preferable that at least one of the ^{two R S} for each of the plurality of Si in the formula (SI-1) is an organic group. It is more preferable that all ^{R S} in the formula (SI-1) are organic groups. In formula (SI-1), n represents an integer of 1 or more, preferably an integer of 1 to 11, more preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 0.

在式（SI-2）中，R^S 分別獨立地表示氫原子或有機基團，R^S 中的至少1個表示有機基團，L¹ 表示直鏈狀或支鏈鏈狀的脂肪族基、環狀的脂肪族基、芳香族基或將該等組合2個以上之基團，L² 表示-Si（R^S ）₂ -、直鏈狀或支鏈鏈狀的脂肪族基、環狀的脂肪族基、芳香族基或將該等組合2個以上之基團，n表示1以上的整數，*分別獨立地表示與其他結構的鍵結部位。 在式（SI-2）中，R^S 及n的含義與上述的式（SI-1）中的R^S 及n相同，較佳態樣亦相同。 在式（SI-2）中，L¹ 係碳數2～20的直鏈的脂肪族基、碳數3～20的支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族烴基或將該等組合2個以上之基團為較佳，碳數2～20的直鏈的脂肪族基為更佳。 在式（SI-2）中，L² 係碳數2～20的直鏈的脂肪族基、碳數3～20的支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族烴基或將該等組合2個以上之基團為較佳，碳數2～20的直鏈的脂肪族基為更佳。 又，L² 係由*¹ -Si（R^S ）₂ -L³ -*² 表示之基團亦較佳。R^S 如上所述，*¹ 表示與式（SI-2）中的氧原子的鍵結部位，L³ 的含義與上述L¹ 相同，較佳態樣亦相同，*² 的含義與式（SI-2）中的L² 所鍵結之*相同。In addition, when R ¹³¹ includes an organically modified (poly)siloxane structure, R ¹³¹ is preferably a structure represented by the following formula (SI-2). [Chemical formula 9]

In formula (SI-2), R ^S each independently represents a hydrogen atom or an organic group, ^{at least one of R S} represents an organic group, L ¹ represents a linear or branched aliphatic group, A cyclic aliphatic group, an aromatic group or a combination of two or more of these groups, L ² represents -Si(R ^S ) ₂ -, linear or branched aliphatic group, cyclic An aliphatic group, an aromatic group, or a group combining two or more of them, n represents an integer of 1 or more, and * each independently represents a bonding site with another structure. In the formula (SI-2), the same R ^S and n (SI-1) in the structured R ^S and n have the meanings above formula, preferred aspects are also the same. In formula (SI-2), L ¹ is a linear aliphatic group with 2 to 20 carbons, a branched aliphatic group with 3 to 20 carbons, and a cyclic aliphatic group with 3 to 20 carbons. , Aromatic hydrocarbon groups having 6 to 20 carbons or a combination of two or more of these groups are preferred, and straight-chain aliphatic groups having 2 to 20 carbons are more preferred. In formula (SI-2), L ² is a linear aliphatic group with 2 to 20 carbons, a branched aliphatic group with 3 to 20 carbons, and a cyclic aliphatic group with 3 to 20 carbons. , Aromatic hydrocarbon groups having 6 to 20 carbons or a combination of two or more of these groups are preferred, and straight-chain aliphatic groups having 2 to 20 carbons are more preferred. Moreover, it is also preferable ^{that L 2} is a group represented by * ¹ -Si(R ^S ) ₂ -L ³ -* ^2. R ^{S is} as described above, * ¹ represents the bonding site with the oxygen atom in formula (SI-2), L ^{3 has} the same meaning as L ¹ above, and the preferred aspect is also the same. * ^{2 has} the same meaning as formula (SI -2) L ² in L 2 is bonded to the same *.

^{Preferably, R 131} in the formula (2-1) is derived from a diamine. Examples of diamines used in the production of alkali-soluble polyimides include linear or branched aliphatic, cyclic aliphatic or aromatic diamines, which are represented by the above formula (SI-2) In the structure, both * are bonded to amine groups, etc. Only one type of diamine may be used, or two or more types may be used.

Specifically, diamines include linear aliphatic groups with 2 to 20 carbons, branched or cyclic aliphatic groups with 3 to 20 carbons, aromatic groups with 6 to 20 carbons, and organic modifications. A diamine having a high-quality (poly)siloxane structure or a combination of two or more groups is preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The linear or branched aliphatic group, the cyclic aliphatic group or the aromatic group may have a substituent. Examples of the substituent include an alkyl group, a hydroxyl group, a thiol group, a carboxyl group, and the above Groups having ethylenically unsaturated bonds, crosslinkable groups other than the above-mentioned ethylenically unsaturated bonds, etc. In addition, a group having an ethylenically unsaturated bond can be introduced by using a diamine having a functional group such as a hydroxyl group, a thiol group, a carboxyl group, etc. to produce polyimide or its precursor compound, and then making it have the same Groups where functional groups react (for example, isocyanate groups, hydroxyl groups, epoxy groups, etc.) and compounds with ethylenically unsaturated bonds react with the above-mentioned polyimide or its precursor compounds. As an example of the group containing an aromatic group, the following groups can be mentioned.

[Chemical formula 10]

In the formula, A is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons that can be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -,- NHC(=O)- or a combination of 2 or more groups of these are preferred, single bond or selected from alkylene groups with 1 to 3 carbons which may be substituted by fluorine atoms, -O-, -C(= The group in O)-, -S- and S(=O) ₂ -is more preferably selected from the group including -CH ₂ -, -O-, -S-, -S(=O) ₂ -, -C The divalent group in the group of (CF ₃ ) ₂ -and -C(CH ₃ ) _{2-is further preferred.}

In addition, among the above-mentioned AR-1 to the above-mentioned AR-10, a structure in which at least one of the hydrogen atoms bonded to the benzene ring is substituted with a hydroxyl group or a thiol group is also preferably mentioned. Among them, the structure in which one or two of the hydrogen atoms in the benzene ring in AR-1～AR-3 are substituted by hydroxyl or thiol group or the bonding in AR-5～AR-10 A structure in which one of the hydrogen atoms of one benzene ring among the two benzene rings and one of the hydrogen atoms bonded to the other benzene ring is substituted by a hydroxyl group or a thiol group is preferable.

As the diamine, specifically selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane Cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis (Aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane or isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 2,5-dihydroxy-p-phenylenediamine, 2,5-dimercapto-p-phenylenediamine, 4 ,4'-diaminodiphenyl or 3,3'-diaminodiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenyl Aminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4,4' -Diaminodiphenyl sulfide or 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3, 3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2 '-Dimethylbiphenyl), 3,3'-Dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis (4-Aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoro Propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4 -Hydroxyphenyl), bis(4-amino-3-hydroxyphenyl), 4,4'-diaminopterphenyl, 4,4'-bis(4-aminophenoxy) Benzene, bis[4-(4-aminophenoxy)phenyl] ash, bis[4-(3-aminophenoxy)phenyl] ash, bis[4-(2-aminophenoxy) ) Phenyl] chrysene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4' -Diaminodiphenyl benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-amine) Phenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-Diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy) Phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4 ,4'-Tetraaminodiphenyl ether, 1,4-bis Aminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)pyridium, 4 ,4'-dimethyl-3,3'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2- (3',5'-Diaminobenzyloxy) ethyl methacrylate, 2,4-diaminocumene or 2,5-diaminocumene, 2,5-dimethyl- P-phenylenediamine, acetguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, 1,3-bis(3- Aminopropyl) tetramethyldisiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diamino Benzaniline, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4- Bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane , 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2 ,2-Bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3 ,5-Bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2 -Trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2 -Trifluoromethylphenoxy) diphenyl sulfite, 4,4'-bis(3-amino-5-trifluoromethylphenoxy) diphenyl sulfite, 2,2-bis[4-( 4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4 '-Diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine and 4,4'-diamino At least one diamine in tetraphenyl.

In addition, the diamines (DA-1) to (DA-18) shown below are also preferable.

[Chemical formula 11]

[Chemical formula 12]

Moreover, as a preferable example, the diamine which has at least 2 alkylene glycol units in a main chain can also be mentioned. Preferably, it is a diamine that contains two or more of ethylene glycol chains and propylene glycol chains or both in combination in one molecule, and more preferably is the above-mentioned diamine and does not contain an aromatic ring. As specific examples, JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR- 148, JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above trade names, manufactured by Huntsman Corporation), 1-(2-(2-(2-aminopropyl) (Oxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc., But it is not limited to these.

The following shows JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( Registered trademark) The structure of EDR-176.

[Chemical formula 13]

In the above, x, y, and z are the arithmetic averages.

From the viewpoint of the flexibility of the cured film obtained, R ¹³¹ in the formula (2-1) is preferably represented by -Ar ⁰ -L ⁰ -Ar ^{0 -.} Ar ^{0 is} each independently an aromatic hydrocarbon group (the carbon number is preferably 6-22, more preferably 6-18, particularly preferably 6-10), and phenylene is preferred. L ⁰ represents a single bond or an aliphatic hydrocarbon group with 1 to 10 carbons which can be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ -, -NHCO- Or these groups can be combined with two or more groups. The meaning of the preferable range of L ⁰ is the same as the above-mentioned A.

From the viewpoint of i-ray transmittance, R ¹³¹ in the formula (2-1) is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and easy availability, the divalent organic group represented by formula (61) is more preferable.

[Chemical formula 14]

In formula (51), R ⁵⁰ to R ⁵⁷ are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, ^{and at least one of R 50} to R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or two Fluoromethyl, trifluoromethyl, phenolic hydroxyl, or thiol group, * each independently represents a bonding site to another structure.

^Examples of the monovalent organic groups of R ⁵⁰ to R 57 include unsubstituted alkyl groups having 1 to 10 carbons (preferably 1 to 6 carbons), and 1 to 10 carbons (preferably carbons 1 to 6) fluorinated alkyl group, phenolic hydroxyl group, thiol group, etc.

[Chemical formula 15]

In the formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

As the diamine compound imparting the structure of formula (51) or (61), dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4, 4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. One of these may be used, or two or more of them may be used in combination.

In addition, the following diamines can also be preferably used. [Chemical formula 16]

-R ¹³² -In the formula (2-1), as ^{the tetravalent organic group represented by R 132 , the same groups as R 115} in the above formula (1-1) can be exemplified, and the preferred range is also the same.

-content- The alkali-soluble polyimide may have only one type of repeating unit represented by the formula (2-1), or may have two or more types. As one embodiment of the alkali-soluble polyimide in the present invention, 50 mol% or more of the total repeating unit can be exemplified, further 70 mol% or more, especially 90 mol% or more, which is derived from the formula (2-1) Represents the alkali-soluble polyimide of the repeating unit. As the upper limit, it is actually 100 mol% or less.

〔Molecular Weight〕 The weight average molecular weight (Mw) of the alkali-soluble polyimide is preferably 2,000 to 500,000, more preferably 2,500 to 100,000, and still more preferably 3,000 to 50,000. In addition, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 1,500 to 50,000, and still more preferably 2,000 to 25,000.

The molecular weight dispersion of the alkali-soluble polyimide is preferably 1.5 to 3.5, and more preferably 2 to 3. In addition, from the viewpoint of developability, the upper limit of the dispersion of the molecular weight of the alkali-soluble polyimide is not particularly limited. For example, 7.0 or less is preferable, 6.5 or less is more preferable, and 6.0 or less is more preferable. In this specification, the degree of molecular weight dispersion means the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

[Specific example] As an alkali-soluble polyimide, for example, the alkali-soluble polyimide used in the Example can be mentioned, but it is not limited to this.

〔resolve resolution〕 For example, the alkali-soluble polyimide can be obtained by the method described in the examples. Specifically, by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine to obtain a precursor compound and then heating, an alkali-soluble polyimide can be obtained. In addition, heating is performed to obtain a precursor compound by reacting a dicarboxylic acid or a dicarboxylic acid derivative (after being halogenated with a halogenating agent) with a diamine, thereby obtaining an alkali-soluble polyimide. When the aforementioned precursor compound or polyimine has functional groups such as hydroxyl, thiol group, carboxyl group, etc., the precursor compound or polyimine is made to have a group that reacts with the aforementioned functional group (for example, isocyanate Group, hydroxyl group, epoxy group, etc.) and ethylenically unsaturated bond compound react with the above polyimide or its precursor compound (in the case of the precursor compound, cyclize by heating etc.), by In this way, polyimides with ethylenically unsaturated bonds can be obtained.

〔Rate of imidization (loop closing ratio)] From the viewpoints of elongation at break and insulating properties of the cured film obtained, the imidization ratio of alkali-soluble polyimide (also referred to as "loop closing ratio") is More than 70% is preferable, more than 80% is more preferable, more than 90% is more preferable. The upper limit of the above-mentioned imidization rate is not particularly limited, and it may be 100% or less. The above-mentioned imidization rate can be measured by, for example, the following method. The infrared absorption spectrum of the alkali-soluble polyimide was measured, and the peak intensity P1 near ^{1377 cm-1, which is an absorption peak derived from the amide structure, was determined.} Next, after the alkali-soluble polyimide was heat-treated at 350°C for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P2 in the vicinity of ^{1377 cm -1 was determined.} Using the obtained peak intensities P1 and P2, the imidization rate of the alkali-soluble polyimide can be determined according to the following formula. The imidization rate (%)=(peak intensity P1/peak intensity P2)×100

〔content〕 The content of the alkali-soluble polyimide in the negative curable composition of the present invention is preferably 20% by mass or more relative to the total solid content of the negative curable composition, more preferably 30% by mass or more, and 40% by mass % Or more is more preferable, and 50 mass% or more is still more preferable. In addition, the content of the alkali-soluble polyimide in the negative curable composition of the present invention is preferably 99.5% by mass or less, and more preferably 99% by mass or less with respect to the total solid content of the negative curable composition. 98% by mass or less is more preferable, 97% by mass or less is still more preferable, and 95% by mass or less is still more preferable. The negative curable composition of the present invention may contain only one kind of alkali-soluble polyimide, or two or more kinds. When two or more are contained, the total amount is preferably in the above-mentioned range.

＜Light radical generator＞ The negative curable composition of the present invention contains a photo radical generator. The photo radical generator is not particularly limited. For example, the photo radical polymerization initiator can be appropriately selected from known compounds. For example, a radical photopolymerization initiator having sensitivity to light from the ultraviolet region to the visible region is preferred. In addition, it can be an active agent that interacts with a light-excited sensitizer and generates active free radicals.

The photoradical generator preferably contains at least one compound having a molar absorption coefficient of ^{at least about 50 L·mol -1} ·cm ^-1 for light with a wavelength in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is better to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) and use an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photo radical generator, any known compound can be used arbitrarily. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazole skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), phosphonium phosphine compounds such as oxyphosphine oxide, hexaaryl bis Oxime compounds such as imidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, Metallocene compounds, organoboron compounds, iron arene complexes, etc. For these details, reference can be made to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A, and paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated into this specification.

As the ketone compound, for example, the compound described in paragraph 0087 of JP-A-2015-087611 can be exemplified, and this content is incorporated in this specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

As the photo-radical generator, hydroxyacetophenone compounds, aminoacetophenone compounds, and phosphine compounds can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A No. 10-291969 and the phosphonium oxide-based initiator described in Japanese Patent No. 4225898 can also be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (brand names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF), Omnirad 907, Omnirad 369, and Omnirad 379 (all manufactured by IGM Resins) can be used. ).

As the aminoacetophenone-based initiator, it is also possible to use the compound described in Japanese Patent Application Laid-Open No. 2009-191179, which has an absorption maximum wavelength matched with a light source of wavelengths such as 365nm or 405nm.

Examples of the phosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, a commercially available product IRGACURE-819 or IRGACURE-TPO (brand name: all made by BASF), Omnirad 819, or Omnirad TPO (all made by IGM Resins) can be used.

As the metallocene compound, IRGACURE-784 (manufactured by BASF Corporation) and the like can be exemplified.

As the photoradical generator, an oxime compound is more preferable. By using an oxime compound, the exposure latitude can be further effectively improved. Among the oxime compounds, the exposure latitude (exposure margin) is relatively wide, and it also functions as a photohardening accelerator, so it is particularly preferred.

As specific examples of the oxime compound, the compound described in JP 2001-233842 A, the compound described in JP 2000-080068 A, and the compound described in JP 2006-342166 A can be used.

As a preferable oxime compound, for example, a compound having the following structure, 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one , 3-Propyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1 -Ketone, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxy Carbonyloxyimino-1-phenylpropan-1-one and the like. In the negative-type curable composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photo-radical generator) as the photo-radical generator. The oxime compound as a light radical generator has a linking group represented by >C=N-O-C(=O)- in the molecule.

[Chemical formula 17]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF), ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, Japan Special Publication 2012-014052) The photo-radical polymerization initiator described in No. 2). In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used.

The oxime compound of the following structure can also be used. [Chemical formula 18]

An oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include the compounds described in JP 2010-262028 A, the compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013 -The compound (C-3) described in paragraph 0101 of Bulletin No. 164471, etc.

As the best oxime compound, oxime compounds with specific substituents shown in Japanese Patent Application Publication No. 2007-269779 or oximes with sulfur aryl groups shown in Japanese Patent Application Publication No. 2009-191061 can be cited Compound etc.

From the viewpoint of exposure sensitivity, the photo-radical generator is selected from the group consisting of trihalomethyl tri ketal compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, and phosphine compounds , Phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene -Iron complexes and their salts, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferably compounds in the group.

Further preferred photo-radical generators are trihalomethyl tri-ketone compounds, α-amino ketone compounds, phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and onium salt compounds , Benzophenone compounds, acetophenone compounds, selected from the group consisting of trihalomethyl tri ketone compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds At least one compound is more preferable, a metallocene compound or an oxime compound is more preferable, and an oxime compound is still more preferable.

In addition, the light radical generator can also use N,N, such as benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. '-Tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-endolinophenyl)-butanone-1, Aromatic ketones such as 2-methyl-1-[4-(methylthio)phenyl]-2-terminal acetone-1, alkylanthraquinones, etc. are quinones formed by condensation of aromatic rings , Benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin, alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. In addition, a compound represented by the following formula (I) can also be used.

[Chemical formula 19]

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbons, an alkyl group having 2 to 20 carbons interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbons, benzene Group or C1-C20 alkyl group, C1-C12 alkoxy group, halogen atom, cyclopentyl, cyclohexyl, C2-C12 alkenyl group, which is substituted by one or more oxygen atoms And at least one substituted phenyl or biphenyl group in the interrupted C2-C18 alkyl group and C1-C4 alkyl group, R ^I01 is a group represented by formula (II), or is The same groups as ^{R I00 , R I02} to R ^I04 are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or a halogen atom.

[Chemical formula 20]

In the formula, R ^I05 to R ^I07 are the same as ^{R I02} to R ^{I04 in the} above formula (I).

In addition, the light radical generator can also use the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

The content of the light radical generator is preferably 0.1-30% by mass relative to the total solid content of the negative curable composition of the present invention, more preferably 0.1-20% by mass, still more preferably 0.5-15% by mass , More preferably, it is 1.0-10 mass %. The light radical generator may contain only one kind, or may contain two or more kinds. When two or more photo-radical generators are contained, the total of them is preferably in the above-mentioned range.

〔Thermal free radical generator〕 The negative curable composition of the present invention may further include a thermal radical generator. The thermal radical generator is a compound that generates free radicals by thermal energy and initiates or promotes the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the radical polymerization reaction proceeds further during heating, and therefore the crosslinking density can sometimes be improved.

Specific examples of the thermal radical generator include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A.

When the thermal radical generator is contained, its content is preferably 0.1 to 30% by mass relative to the total solid content of the negative curable composition of the present invention, more preferably 0.1 to 20% by mass, and still more preferably 5 to 15% by mass. The thermal radical generator may contain only one type or two or more types. When two or more thermal radical generators are contained, it is preferable that the total thereof is in the above-mentioned range.

＜Specific bifunctional crosslinking agent＞ The negative-type curable composition of the present invention contains a bifunctional crosslinking agent (specific bifunctional crosslinking agent) that does not have a cyclic structure based on covalent bonds at positions other than polymerized groups and the distance between the polymerized groups is 12 atoms or more. Coupling agent). The bifunctional crosslinking agent refers to a crosslinking agent having two polymerizing groups.

In the specific bifunctional crosslinking agent, examples of the polymerizing group include cyclic ether groups such as ethylenically unsaturated groups, epoxy groups, and oxetanyl groups, and alkoxymethyl groups such as methoxymethyl groups. Contains alkoxy, hydroxymethyl, etc. As the polymerizing group, the specific bifunctional crosslinking agent may contain two different types of polymerizing groups, and it is preferable to include two types of polymerizing groups of the same type. Examples of the cyclic structure based on the covalent bond include an aromatic cyclic hydrocarbon ring structure, an aliphatic hydrocarbon ring structure, an aromatic heterocyclic structure, and an aliphatic heterocyclic structure. The absence of a cyclic structure based on a covalent bond at a position other than a polymerized group means the case where the polymerized group may have a cyclic structure based on a covalent bond such as a cyclic ether group, but in addition to two polymerized groups The part other than the group does not have a ring structure based on a covalent bond.

The distance between the polymer groups refers to the number of atoms included between the above-mentioned polymer groups, and when calculating the above-mentioned number of atoms, it is assumed that the atoms included in the above-mentioned polymer groups are not included. When the polymerized group is an ethylenically unsaturated group or a cyclic ether group, the distance between the polymerized groups refers to the smallest number of atoms connecting to the branch point of the polymer chain formed by polymerization and the branch point of other polymer chains When calculating the number of atoms, it is assumed that the atoms contained in the branch points are not included. When the polymer group is an alkoxy group such as a methoxy group or a methylol group, the distance between the polymer groups refers to the connection between the oxygen atom contained in one polymer group and the oxygen atom contained in the other polymer group. The smallest number among the number of oxygen atoms, and the above-mentioned oxygen atom is not included in the calculation of the above-mentioned atomic number. In the following formulas, the atoms marked with numbers in italics are the atoms included in the calculation of the distance of the polymerized group. For example, in the compound represented by the following formula (B-3), the distance between the polymer groups is 15 atoms, and in the compound represented by the following formula (B-5), the distance between the polymer groups is 12 Atom, in the compound represented by the following formula (B-9), the distance between the polymer groups is 10 atoms, and in the compound represented by the following formula (D-2), the distance between the polymer groups is 15 Atom, in the compound represented by the following formula (K-1), the distance between the polymeric groups is 12 atoms. [Chemical formula 21]

The distance between the aforementioned polymeric groups may be 12 atoms or more, preferably 12 to 50 atoms, and more preferably 14 to 30 atoms.

When the polymer group is an ethylenically unsaturated group, the specific bifunctional crosslinking agent includes a vinyl group, an allyl group, a vinyl phenyl group, a (meth)acrylamido group, or a group containing the polymer group. A (meth)acryloyloxy group is preferable, a (meth)acryloyloxy group is more preferable, and a methacryloyloxy group is more preferable. In addition, when the polymerizable group is an ethylenically unsaturated group, the polymerizable group is preferably a radical polymerizable group. When the above-mentioned polymeric group is a cyclic ether group, as the group containing the above-mentioned polymeric group, the specific bifunctional crosslinking agent preferably includes an epoxy-containing group or an oxetanyl-containing group, including The glycidyl group is more preferable. When the above-mentioned polymeric group is an alkoxy group or a methylol group, the group containing the polymeric group is preferably an alkoxymethyl group or a methylol group, and more preferably a methoxymethyl group or a methylol group.

在式（P1）及式（P2）中、*表示與其他結構的鍵結部位。The specific bifunctional crosslinking agent preferably contains a polyoxyalkylene group. In addition, it is preferable that the two polymer groups in the specific bifunctional crosslinking agent are connected by a structure containing a polyoxyalkylene group. In the present invention, a polyoxyalkylene group refers to a group to which two or more oxyalkylene groups are directly bonded. The alkylene groups of the plurality of oxyalkylene groups contained in the polyoxyalkylene group may be the same or different, respectively. When the polyoxyalkylene group contains a plurality of oxyalkylene groups with different alkylene groups, the arrangement of the oxyalkylene groups in the polyoxyalkylene group may be a random arrangement, a block arrangement, or an alternating arrangement. Arrangement of other patterns. The carbon number of the above-mentioned alkylene group (when the alkylene group has a substituent, including the carbon number of the substituent) is preferably 2 or more, more preferably 2-50, more preferably 2-30, more preferably 2-10, Preferably, 2 to 6 are more preferred, 2 to 4 are particularly preferred, and 2 or 3 is the most preferred. In addition, the above-mentioned alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. can be mentioned. In addition, the number of oxyalkylene groups contained in the polyoxyalkylene group (the number of repetitions of the polyoxyalkylene group) is preferably 2-100, more preferably 2-50, more preferably 2-30, and 2-10 It is particularly good, and 3～10 is the best. As a polyoxyethylene group, from the viewpoint of increasing the elongation at break, polyoxyethylene, polyoxypropylene, polyoxytrimethylene, polyoxytetramethylene, or plural oxyethylene groups and plural The group formed by bonding oxyethylene group is preferable, polyoxyethylene group or polyoxypropylene group is more preferable, and polyoxyethylene group is further preferable. Among the above-mentioned groups where a plurality of oxyethylene groups are bonded to a plurality of oxypropylene groups, the oxyethylene groups and the oxypropylene groups can be arranged randomly, can be arranged in blocks, or can be arranged in alternating patterns. . Preferred aspects of the number of repetitions of oxyethylene and the like in these groups are as described above. In addition, the oxypropylene group contained in the polyoxyethylene group or the group formed by bonding the plurality of oxyethylene group and the plurality of oxyethylene group may be independently 1-methyloxyethylene group. (Following formula (P1)) and either of 2-methyloxyethylene (Following formula (P2)). [Chemical formula 22]

In formula (P1) and formula (P2), * represents the bonding site with other structures.

The specific bifunctional crosslinking agent preferably contains a compound that causes a polymerization reaction by the photosensitivity of the above-mentioned photopolymerization initiator. Specifically, it is preferable that the photopolymerization initiator is a photoradical polymerization initiator and the bifunctional crosslinking agent is a radical crosslinking agent, and the photopolymerization initiator is a photoradical polymerization initiator and The specific bifunctional crosslinking agent is preferably a compound containing two radical polymerizable groups, that is, an ethylenically unsaturated group, as the polymerizing group. The photopolymerization initiator is a photoradical polymerization initiator and the specific The bifunctional crosslinking agent is further preferably a compound containing two (meth)acryloxy groups as the polymerizing group.

The specific bifunctional crosslinking agent preferably contains a thermal crosslinking agent. As a thermal crosslinking agent, that is, a specific bifunctional crosslinking agent, a compound containing two groups selected from the group consisting of the above-mentioned cyclic ether group, alkoxy group and methylol group as the polymerizing group is preferred, A compound containing 2 epoxy groups, oxetanyl groups, alkoxymethyl or methylol groups as the polymerizing group is more preferred, and the compound containing 2 glycidyl groups or methylol groups as the polymerizing group is Further better.

The molecular weight of the specific bifunctional crosslinking agent is preferably 200 to 2,000, more preferably 250 to 1,000, and even more preferably 250 to 800.

Specific examples of the specific bifunctional crosslinking agent include polyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate and polypropylene glycol di(meth)acrylate. Alkylene glycol di(meth)acrylate, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and other polyalkylene glycol diglycidyl ethers, alkylene diglycidyl ethers Among compounds such as alcohol diepoxypropyl ether, the distance between the above-mentioned polymeric groups is 12 atoms or more. Among these, from the viewpoint of increasing the elongation at break of the cured film obtained, as a specific bifunctional crosslinking agent, polyalkylene glycol di(meth)acrylate or polyalkylene glycol bicyclic Oxypropyl ether is preferred, and polyalkylene glycol di(meth)acrylate is more preferred. The repeating number of the alkylene glycol unit in the polyalkylene glycol di(meth)acrylate or polyalkylene glycol diglycidyl ether is preferably 3-16, and 3-6 is Better. The alkylene glycol unit in the above-mentioned polyalkylene glycol di(meth)acrylate or polyalkylene glycol diglycidyl ether is preferably an ethylene glycol unit or a propylene glycol unit. The unit is better.

The content of the specific bifunctional crosslinking agent is preferably 1 to 60% by mass with respect to the total solid content of the negative curable composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 30% by mass or less. The negative curable composition of the present invention may contain only one type of specific bifunctional crosslinking agent, or may contain two or more types. When two or more types of specific bifunctional crosslinking agents are contained, it is preferable that the total thereof is in the above-mentioned range.

＜Other free radical crosslinking agents＞ It is preferable that the negative curable composition of the present invention further contains a radical crosslinking agent other than the specific bifunctional crosslinking agent. In the present invention, the compound conforming to the specific bifunctional crosslinking agent is set to not conform to other free radical crosslinking agents. That is, other free radical crosslinking agents are free radical crosslinking agents other than bifunctional or the above-mentioned free radical crosslinking agent whose distance between the polymer groups is less than 12 atoms. Other radical crosslinkers are compounds with radical polymerizable groups. As the radical polymerizable group, a group containing an ethylenically unsaturated bond is preferred. Examples of the group containing the above-mentioned ethylenically unsaturated bond include groups having an ethylenically unsaturated bond, such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth)acryloyl group. Among these, as the group containing the above-mentioned ethylenically unsaturated bond, a (meth)acryloyl group is preferable, and from the viewpoint of reactivity, a (meth)acryloyloxy group is more preferable.

The other radical crosslinking agent may be a compound having one or more ethylenic unsaturated bonds, and a compound having two or more is more preferable. The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above-mentioned ethylenically unsaturated bond. Moreover, from the viewpoint of the elongation at break of the cured film obtained, the negative curable composition of the present invention preferably contains three or more compounds having ethylenic unsaturated bonds as other radical crosslinking agents. As a compound having 3 or more of the above-mentioned ethylenically unsaturated bonds, a compound having 3 to 15 ethylenic unsaturated bonds is preferred, and a compound having 3 to 10 ethylenic unsaturated bonds is more preferred, with 3 to 15 ethylenic unsaturated bonds being more preferred. Compounds with 6 ethylenically unsaturated bonds are more preferred. In addition, the compound having 3 or more of the above-mentioned ethylenic unsaturated bonds is preferably a compound having 3 or more of the groups containing the above-mentioned ethylenic unsaturated bond, and a compound having 3 to 15 is more preferred, with 3 to 15 10 compounds are more preferred, and compounds with 3 to 6 are particularly preferred. In addition, from the viewpoint of the elongation at break of the cured film obtained, the negative curable composition of the present invention includes a compound having two ethylenic unsaturated bonds and a compound having three or more ethylenic unsaturated bonds. For better.

The molecular weight of other radical crosslinking agents is preferably 2,000 or less, more preferably 1,500 or less, and more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

As specific examples of other radical crosslinking agents, unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, The amides are preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reactants of unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amino groups, sulfhydryl groups, and monofunctional or polyfunctional isocyanates or epoxy groups can also be preferably used, Dehydration condensation reaction product with monofunctional or polyfunctional carboxylic acid, etc. In addition, an addition reaction product of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and further having halogen groups Or a substitution reaction product of unsaturated carboxylic acid esters or amides with detachable substituents such as toluene sulfonyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols. As another example, instead of the above-mentioned unsaturated carboxylic acid, a group of compounds substituted with unsaturated phosphonic acid, vinyl benzene derivatives such as styrene, vinyl ether, allyl ether, and the like can be used. As a specific example, the description in paragraphs 0113 to 0122 of JP 2016-027357 A can be referred to, and these contents are incorporated in this specification.

In addition, other radical crosslinking agents are preferably compounds having a boiling point of 100°C or higher under normal pressure. As an example, diethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentaerythritol tri (Meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dine pentaerythritol penta (meth) acrylate, dine pentaerythritol hexa (meth) acrylate, hexanediol (meth) Base) acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. in multifunctional alcohol Compounds in which ethylene oxide or propylene oxide is added and then (meth)acrylated, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Application Publication No. 51-037193, etc. The (meth)acrylic urethanes described in the gazette, the polyester acrylates described in the respective gazettes of JP Sho 48-064183, JP Sho 49-043191, and JP Sho 52-030490, Polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid; and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of JP 2008-292970 A are also preferable. Moreover, the polyfunctional (meth)acrylate etc. which are obtained by making the compound which has a cyclic ether group and ethylenically unsaturated bond, such as a polyfunctional carboxylic acid and glycidyl (meth)acrylate react, are mentioned.

In addition, as other preferred free radical crosslinking agents other than the above, it is also possible to use those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216, etc. , And has 2 or more compounds with ethylenically unsaturated bonds or cardo resins.

Furthermore, as other examples, there are specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and Japanese Patent Application Publication No. 02- Vinylphosphonic acid-based compounds described in 025493 No. Bulletin, etc. In addition, the perfluoroalkyl group-containing compound described in JP 61-022048 A can also be used. Furthermore, it is also possible to use those introduced as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pages 300 to 308 (1984).

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Unexamined Patent Publication No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and these contents are incorporated herein. In the manual.

In addition, the following compounds described as formula (1) and formula (2) together with specific examples in Japanese Patent Application Laid-Open No. 10-062986 can also be used as other radical crosslinking agents. This compound is added to a polyfunctional alcohol. It is a compound formed by (meth)acrylate esterification after ethylene oxide or propylene oxide.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as other radical crosslinking agents, and these contents are incorporated in this specification.

As a free radical crosslinking agent, dineopentaerythritol triacrylate (as a commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dineopentaerythritol tetraacrylate (as a commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dineopentaerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), dineopentol hexa(other meth)acrylate (as a commercial product is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin- Nakamura Chemical Co., Ltd. (manufactured by Nakamura Chemical Co., Ltd.) and a structure in which these (meth)acrylic groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

As commercial products of other free radical crosslinking agents, for example, SR-494, which is a 4-functional acrylate having 4 ethoxyl chains, manufactured by Sartomer Company, Inc, and 231, manufactured by Sartomer Company, Inc. 239, manufactured by Nippon Kayaku Co., Ltd. as a 6-functional acrylate with 6 pentoxy chains, DPCA-60, as a 3-functional acrylate with 3 isobutoxy chains, TPA-330, Urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA -7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI- 600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As other free radical crosslinking agents, such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Application Publication No. 02-016765 Urethane acrylates, Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 have epoxy resins. Urethane compounds with an ethane-based skeleton are also preferred. Furthermore, as other radical crosslinking agents, it is also possible to use those described in JP-A 63-277653, JP-A 63-260909, and JP-A 01-105238 that have an amine group in the molecule. Structure or sulfide structure compound.

Other free radical crosslinking agents may be free radical crosslinking agents having acid groups such as carboxyl groups and phosphoric acid groups. Among the radical crosslinking agents with acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred. The unreacted hydroxyl groups of the aliphatic polyhydroxy compounds are reacted with non-aromatic carboxylic acid anhydrides to form an acid group. The free radical crosslinking agent is more preferable. Particularly preferably, the unreacted hydroxyl group of the aliphatic polyhydroxy compound reacts with the non-aromatic carboxylic anhydride to have an acid group. Among the free radical crosslinking agents, the aliphatic polyhydroxy compound is one of neopentaerythritol or dineopentaerythritol. Compound. As a commercially available product, for example, M-510, M-520, etc. are mentioned as polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd..

The preferred acid value of the free radical crosslinking agent with an acid group is 0.1-40 mgKOH/g, particularly preferably 5-30 mgKOH/g. As long as the acid value of the radical crosslinking agent is within the above-mentioned range, the workability in production is excellent, and the developability is also excellent. On the other hand, from the viewpoint of the development speed during alkali development, the acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, and particularly preferably 1 to 100 mgKOH/g. In addition, the polymerizability is good. The above acid value is measured in accordance with the description of JIS K 0070:1992.

In the negative curable composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as another radical crosslinking agent from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the cured film. As a monofunctional free radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy Ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. (meth) Acrylic acid derivatives, N-vinylpyrrolidone, N-vinylcaprolactam and other N-vinyl compounds, allyl glycidyl ether, diallyl phthalate, trimellitic acid Allyl compounds such as allyl esters, etc. As a monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100°C or higher under normal pressure is also preferable.

As another radical crosslinking agent, it is preferable to use a bifunctional methacrylate or acrylate from the viewpoint of the resolution of the pattern and the stretchability of the film. As the specific compound of the specific bifunctional crosslinking agent or other free radical crosslinking agent, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate can be used. Glycol diacrylate, PEG200 diacrylate (polyethylene glycol diacrylate and polyethylene glycol chain formula weight is about 200), PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethyl Acrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5- Pentylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tri Cyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct of bisphenol A two Acrylate, EO adduct of bisphenol A, dimethacrylate, 2-hydroxy-3-propenoxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid Modified dimethacrylates, other bifunctional acrylates with urethane bonds, and bifunctional methacrylates with urethane bonds. These can be used by mixing two or more types as needed. Moreover, as a radical crosslinking agent more than bifunctional, diallyl phthalate, triallyl trimellitate, etc. are mentioned.

When other radical crosslinking agents are contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the negative curable composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and more preferably 30% by mass or less.

The radical crosslinking agent may be used singly or as a mixture of two or more. When two or more types are used at the same time, the total amount is preferably in the above range.

＜Other thermal crosslinking agents＞ The negative curable composition of the present invention may contain other thermal crosslinking agents. In the present invention, the compound conforming to the specific bifunctional crosslinking agent is set to not conform to other thermal crosslinking agents. That is, the other thermal crosslinking agent is a thermal crosslinking agent other than bifunctional or a thermal crosslinking agent whose distance between the above-mentioned polymeric groups is less than 12 atoms. As other thermal crosslinking agents, as long as there are a plurality of other compounds in the composition or their reaction products in the molecule to form a covalent bond between the compound is promoted by the action of an acid, there is no special As a limitation, a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl is preferred, and it has at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl Compounds in which the group is directly bonded to the nitrogen atom are more preferred. As other thermal crosslinking agents, the following compounds can be mentioned, for example, having melamine, acetylene carbamide, urea, alkylene urea, benzoguanamine and other amino group-containing compounds reacting with formaldehyde or reacting formaldehyde with alcohol and using hydroxyl A compound having a structure in which a methyl group or an alkoxymethyl group replaces the hydrogen atom of the above-mentioned amino group. The method for producing these compounds is not particularly limited, as long as they have the same structure as the compound produced by the above-mentioned method. In addition, it may be an oligomer in which the methylol groups of these compounds are self-condensed with each other. As the above-mentioned amine-containing compound, the thermal crosslinking agent using melamine is called melamine-based crosslinking agent, and the thermal crosslinking agent using acetylene carbamide, urea or alkylene urea is called urea-based crosslinking agent. The thermal crosslinking agent of alkylene urea is called alkylene urea crosslinking agent, and the one that uses benzoguanamine is called benzoguanamine crosslinking agent. Among them, the negative curable composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent. The crosslinking agent and at least one compound from the group of the melamine-based crosslinking agent are more preferable.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like.

Specific examples of urea-based crosslinking agents include, for example, monomethylolated acetylene carbamide, dimethylolated acetylene carbamide, trimethylolated acetylene carbamide, tetramethylolated acetylene carbamide, and monomethoxymethylated acetylene carbamide. Methylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetramethoxymethylated acetylene carbamide, monomethoxymethylated acetylene carbamide, dimethoxy Methylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetraethoxymethylated acetylene carbamide, monopropoxymethylated acetylene carbamide, dipropoxymethylated acetylene carbamide, tripropoxymethylated acetylene carbamide Alkylated acetylene carbamide, tetrapropoxymethylated acetylene carbamide, monobutoxymethylated acetylene carbamide, dibutoxymethylated acetylene carbamide, tributoxymethylated acetylene carbamide or tetrabutoxymethylated acetylene carbamide Acetylene carbamide crosslinking agents such as acetylated acetylene carbamide; Urea crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, Monomethylolated ethylene urea or dimethylolated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxy Methylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea, etc. Coupling agent, Monomethylolated propylene urea, dimethylolated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxy Propylene urea such as methylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea Crosslinking agent, 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole Pyridone and so on.

As specific examples of the benzoguanamine-based crosslinking agent, for example, monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, tetramethylol Methylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated Benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine Amine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, Monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

In addition, as a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl, it is also possible to preferably use a compound selected from the group consisting of hydroxymethyl and alkoxymethyl A compound in which at least one group is directly bonded to an aromatic ring (preferably a benzene ring). Specific examples of such compounds include terephthalic methanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl) Methyl) benzophenone, hydroxymethyl hydroxymethyl benzoate, hydroxymethyl benzene, bis(hydroxymethyl) biphenyl, dimethyl bis(hydroxymethyl) biphenyl, bis(methoxymethyl) benzene, double (Methoxymethyl) cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methyl Methoxymethylbenzene, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylene Tris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy- 1,3-terephthalene dimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As other thermal crosslinking agents, commercially available products can be used. Preferred commercially available products include 46DMOC, 46DMOEP (above, manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP , DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, the same below) MX-290, NIKALACMX-280, NIKALACMX-270, NIKALACMX-279, NIKALACMW-100LM, NIKALACMX-750LM (above, SANWA CHEMICAL CO., LTD System) and so on.

In addition, the negative curable composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzophenone compounds as other thermal crosslinking agents.

[Epoxy compounds (compounds with epoxy groups)] As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy group undergoes a crosslinking reaction below 200°C, and it is unlikely to cause film shrinkage because it does not undergo a dehydration reaction due to crosslinking. Therefore, containing the epoxy compound is effective in suppressing the low-temperature hardening and warpage of the negative-type curable composition.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the modulus of elasticity is further reduced, and warpage can be suppressed. The polyethylene oxide group means the number of repeating units of ethylene oxide of 2 or more, and the number of repeating units is preferably 2-15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and ethylene glycol bicyclic Alkylene glycol type epoxy resins or polyol hydrocarbons such as oxypropyl ether, butylene glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, etc. Type epoxy resin; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; epoxy-containing silicone such as polymethyl (glycidoxypropyl) silicone, etc., but It is not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered Trademarks) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) ) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740, RIKARESIN (registered trademark) BEO-20E (the above product name, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (commodity Name, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above product names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081 , CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (above trade name, manufactured by DAICEL CORPORATION), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN -104S, CER-1020, EPPN-201, BREN-S, BREN-10S (trade names above, manufactured by Nippon Kayaku Co., Ltd.), etc. Among them, from the viewpoints of suppressing warpage and excellent heat resistance, epoxy resins containing polyethylene oxide groups are preferred. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups and are therefore preferred.

[Oxetane compounds (compounds with oxetanyl groups)] Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxetane, and 1,4-bis{ [(3-Ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl] ester and the like. As a specific example, the ARON OXETANE series manufactured by TOAGOSEI CO., LTD. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or in combination. the above.

〔Benzo 㗁 𠯤 compounds (compounds with benzo azole group)〕 The benzoglucan compound is preferred because of the cross-linking reaction derived from the ring-opening addition reaction and does not produce outgassing during hardening, thereby reducing thermal shrinkage and suppressing warpage.

As preferred examples of the benzoglyph compound, Ba-type benzoglyph, Bm-type benzoglyph, Pd-type benzoglyph, Fa-type benzoglyph (the above product name, manufactured by Shikoku Chemicals Corporation) ), polyhydroxystyrene resin benzo 㗁 adduct, novolak type dihydro benzo 㗁 𠯤 compound. These can be used alone, or two or more of them can be mixed.

The content of the other thermal crosslinking agent is preferably 0.1-30% by mass relative to the total solid content of the negative curable composition of the present invention, more preferably 0.1-20% by mass, and still more preferably 0.5-15% by mass , 1.0-10% by mass is particularly preferred. The thermal crosslinking agent may contain only one kind, or may contain two or more kinds. When two or more thermal crosslinking agents are contained, the total of them is preferably within the above-mentioned range.

＜Solvent＞ The negative curable composition of the present invention preferably contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfenes, amines, and alcohols.

As esters, for example, preferred ones include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, pentyl formate, isoamyl acetate, butyl propionate, and isopropyl butyrate. , Ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetate (for example, alkoxy Methyl acetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxy Ethyl acetate, etc.)), 3-alkoxypropionic acid alkyl esters (for example, 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionate ( For example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate Ester and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.) , Methyl Pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Methyl Acetate, Ethyl Acetate, Methyl 2-oxobutyrate, Ethyl 2-oxobutyrate, Ethyl Caproate , Ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve acetic acid. Ester, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ethyl Ester, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, etc. are preferable.

The ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucanone, and dihydrolevorotone. Glucanone and the like are preferable.

Examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and terpenes such as limonene.

As the sulfenite, for example, dimethyl sulfenite is preferable.

Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. Amine, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, etc. The best.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methyl Oxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether Base ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl benzyl alcohol, n-pentanol , Methyl pentanol and diacetone alcohol, etc.

Regarding the solvent, from the viewpoint of improvement of the properties of the coating surface, etc., a form in which two or more types are mixed is also preferable.

In the present invention, it is selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, acetic acid Butyl ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfene, ethyl carbitol acetate, butyl card One solvent or a mixed solvent composed of two or more of the alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. It is particularly preferable to use dimethyl sulfoxide and γ-butyrolactone at the same time.

Regarding the content of the solvent, from the viewpoint of coatability, it is preferable that the total solid content concentration of the negative curable composition of the present invention is 5 to 80% by mass, and it is preferably 5 to 75% by mass. The amount is more preferable, and it is more preferable to set it to 10 to 70% by mass, and it is still more preferable to set it to 40 to 70% by mass. The solvent content can be adjusted according to the required thickness of the coating film and the coating method.

The solvent may contain only one type or two or more types. When two or more kinds of solvents are contained, the total of them is preferably in the above range.

<Compounds with sulfonamide structure, compounds with thiourea structure> From the viewpoint of improving the adhesion of the obtained cured film to the substrate, the negative curable composition of the present invention further comprises a compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure At least one compound is preferred.

在式（S-1）中，R表示氫原子或有機基團，R可以與其他結構鍵結而形成環結構，*分別獨立地表示與其他結構的鍵結部位。 上述R係與下述式（S-2）中的R² 相同的基團為較佳。 具有磺醯胺結構之化合物可以為具有2個以上磺醯胺結構之化合物，具有1個以上磺醯胺結構之化合物為較佳。[Compound with sulfonamide structure] The sulfonamide structure is a structure represented by the following formula (S-1). [Chemical formula 23]

In formula (S-1), R represents a hydrogen atom or an organic group, R may be bonded to another structure to form a ring structure, and * each independently represents a bonding site to another structure. The above-mentioned R system is preferably the same as ^{R 2} in the following formula (S-2). The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, and a compound having more than one sulfonamide structure is preferred.

在式（S-2）中，R¹ 、R² 及R³ 分別獨立地表示氫原子或1價有機基團，R¹ 、R² 及R³ 中的2個以上可以相互鍵結而形成環結構。 R¹ 、R² 及R³ 分別獨立地表示1價有機基團為較佳。 作為R¹ 、R² 及R³ 的例子，可舉出氫原子或烷基、環烷基、烷氧基、烷基醚基、烷基矽基、烷氧基矽基、芳基、芳基醚基、羧基、羰基、烯丙基、乙烯基、雜環基、或者將該等組合2個以上之基團等。 作為上述烷基，碳數1～10的烷基為較佳，碳數1～6的烷基為更佳。作為上述烷基，例如，可舉出甲基、乙基、丙基、丁基、戊基、己基、異丙基、2-乙基己基等。 作為上述環烷基，碳數5～10的環烷基為較佳，碳數6～10的環烷基為更佳。作為上述環烷基，例如，可舉出環丙基、環丁基、環戊基及環己基等。 作為上述烷氧基，碳數1～10的烷氧基為較佳，碳數1～5的烷氧基為更佳。作為上述烷氧基，可舉出甲氧基、乙氧基、丙氧基、丁氧基及戊氧基等。 作為上述烷氧基矽基，碳數1～10的烷氧基矽基為較佳，碳數1～4的烷氧基矽基為更佳。作為上述烷氧基矽基，可舉出甲氧基矽基、乙氧基矽基、丙氧基矽基及丁氧基矽基等。 作為上述芳基，碳數6～20的芳基為較佳，碳數6～12的芳基為更佳。上述芳基可具有烷基等取代基。作為上述芳基，可舉出苯基、甲苯基、二甲苯基及萘基等。 作為上述雜環基，可舉出從三唑環、吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡唑環、異㗁唑環、異噻唑環、四唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、哌啶環、哌𠯤環、口末啉環、二氫哌喃環、四氫哌喃環、三𠯤環等雜環結構去除1個氫原子之基團等。The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [Chemical formula 24]

In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, ^{and two or more of R 1} , R ² and R ³ may be bonded to each other to form a ring structure. Preferably, R ¹ , R ² and R ³ each independently represent a monovalent organic group. Examples of R ¹ , R ² and R ³ include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, and an aryl group. Ether group, carboxyl group, carbonyl group, allyl group, vinyl group, heterocyclic group, or a combination of two or more of these groups, etc. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, 2-ethylhexyl group etc. are mentioned, for example. As the above-mentioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. As said cycloalkyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. are mentioned, for example. As the above-mentioned alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. are mentioned. As the above-mentioned alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned. As the above-mentioned aryl group, an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 12 carbon atoms is more preferred. The above-mentioned aryl group may have a substituent such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned. Examples of the above heterocyclic group include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetrazole ring, Heterocyclic structures such as pyridine ring, pyrimidine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, porphyrin ring, dihydropiperan ring, tetrahydropiperan ring, trihydropyran ring and other heterocyclic structures remove 1 hydrogen Groups of atoms, etc.

Among these, ^{compounds in which R 1} is an aryl group and R ² and R ³ are each independently a hydrogen atom or an alkyl group are preferred.

Examples of compounds having a sulfonamide structure include toluenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, Hydroxynaphthyl sulfonamide, naphthyl-1-sulfonamide, naphthyl-2-sulfonamide, m-nitrobenzene sulfonamide, p-chlorobenzene sulfonamide, toluene sulfonamide, N,N-di Methanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide , N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide, etc.

在式（T-1）中，R⁴ 及R⁵ 分別獨立地表示氫原子或1價有機基團，R⁴ 及R⁵ 可以鍵結而形成環，R⁴ 可以與*所鍵結之其他結構鍵結而形成環結構，R⁵ 可以與*所鍵結之其他結構鍵結而形成環結構，*分別獨立地表示與其他結構的鍵結部位。[Compound with thiourea structure] The thiourea structure is a structure represented by the following formula (T-1). [Chemical formula 25]

In formula (T-1), R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent organic group, R ⁴ and R ⁵ can be bonded to form a ring, and R ⁴ can be bonded to other structures with * Bonded to form a ring structure, R ⁵ can be bonded to other structures to which * is bonded to form a ring structure, and * independently represents a bonding site with other structures.

Preferably, R ⁴ and R ⁵ are each independently a hydrogen atom. Examples of R ⁴ and R ⁵ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, A carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a combination of two or more of these groups, etc. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable. As said alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, 2-ethylhexyl group etc. are mentioned, for example. As the above-mentioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. As said cycloalkyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. are mentioned, for example. As the above-mentioned alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable. As said alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, etc. are mentioned. As the above-mentioned alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable. As said alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, a butoxysilyl group, etc. are mentioned. As the above-mentioned aryl group, an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 12 carbon atoms is more preferred. The above-mentioned aryl group may have a substituent such as an alkyl group. As said aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, etc. are mentioned. Examples of the above heterocyclic group include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetrazole ring, Heterocyclic structures such as pyridine ring, pyrimidine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, porphyrin ring, dihydropiperan ring, tetrahydropiperan ring, trihydropyran ring and other heterocyclic structures remove 1 hydrogen Groups of atoms, etc. The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferred.

在式（T-2）中，R⁴ ～R⁷ 分別獨立地表示氫原子或1價有機基團，R⁴ ～R⁷ 中的至少2個可以相互鍵結而形成環結構。The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [Chemical formula 26]

In formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, ^{and at least two of R 4} to R ⁷ may be bonded to each other to form a ring structure.

In formula (T-2), the same as R (T-1) and the meanings of R ⁴ and R ⁵ of the formula ⁴ and R ^5, preferred aspects are also the same. In the formula (T-2), it ^{is preferable that R 6} and R ⁷ are each independently a monovalent organic group. In the formula (T-2), the preferred aspect of the monovalent organic group in ^{R 6} and R ^{7 is the same as that of the monovalent organic group in R 4} and R ⁵ in the formula (T-1) The appearance is the same.

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1- Adamantylthiourea, N-benzylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diiso Propylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylene thiourea (2-imidazoline thione), Carbimazole, 1,3-dimethyl-2-thiohydantoin, etc.

〔content〕 The total content of the compound having a sulfonamide structure and the compound having a thiourea structure relative to the total mass of the negative curable composition of the present invention is preferably 0.05-10% by mass, more preferably 0.1-5% by mass , 0.2 to 3% by mass is more preferable. The negative-type curable composition of the present invention may include only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may include two or more. When only one type is included, the content of the compound is within the above-mentioned range, and when two or more types are included, the total amount of the compound is preferably within the above-mentioned range.

＜Migration inhibitor＞ The negative-type curable composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the transfer of metal ions originating from the metal layer (metal wiring) into the negative-type curable composition layer.

The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoazole ring, isothiazole ring, tetra Azole ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, oromoline ring, 2H-piperan ring and 6H-piperan ring, tricyclic ring) compounds, with Thiourea and sulfhydryl-based compounds, hindered phenolic compounds, salicylic acid derivative compounds, and hydrazine derivative compounds. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Alternatively, an ion scavenger that traps anions such as halogen ions can also be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711, and JP 2011-059656 can be used. The compound described in paragraph 0052 of JP-A-2012-194520, the compound described in paragraphs 0114, 0116, and paragraph 0118 of JP 2012-194520 A, the compound described in paragraph 0166 of International Publication No. 2015/199219, and the like.

As specific examples of migration inhibitors, the following compounds can be given.

[Chemical formula 27]

When the negative type curable composition has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the negative type curable composition is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% by mass is more preferable.

There may be only one type of migration inhibitor, or two or more types. When there are two or more migration inhibitors, the total of them is preferably in the above-mentioned range.

＜Polymerization inhibitor＞ The negative-type curable composition of the present invention preferably contains a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tertiary butyl-p-cresol, gallic phenol, and p-tertiary butylcatechol can be preferably used. , 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4- Methyl-6-tertiary butyl phenol), N-nitrosophenylhydroxylamine trivalent cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, phenothionine, N-nitroso Diphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tertiary butyl-4 -Methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N- Ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tertiarybutyl)phenylmethane , 1,3,5-tris(4-tertiary butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6-(1H, 3H , 5H)-Triketone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical, 1,1-diphenyl-2-picrylhydrazino, dibutyl dithio Copper (II) carbamate, nitrobenzene, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitroso-N-phenylhydroxyamine ammonium salt, etc. In addition, the polymerization inhibitor described in paragraph 0060 of JP 2015-127817 A and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

In addition, the following compounds (Me is a methyl group) can be used.

[Chemical formula 28]

When the negative-type curable composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the negative-type curable composition of the present invention can be, for example, 0.01 to 20.0% by mass, 0.01 -5% by mass is preferable, 0.02-3% by mass is more preferable, and 0.05-2.5% by mass is still more preferable. In addition, when the storage stability of the negative-type curable composition solution is required, it may preferably be 0.02 to 15.0% by mass, and in this case, it is more preferably 0.05 to 10.0% by mass.

There may be only one type of polymerization inhibitor, or two or more types. When there are two or more kinds of polymerization inhibitors, it is preferable that the total of them is in the above-mentioned range.

＜Metal adhesion improver＞ The negative-type curable composition of the present invention preferably contains a metal adhesion improver for improving adhesion with metal materials used for electrodes, wiring, and the like. Examples of metal adhesion improvers include silane coupling agents, aluminum-based adhesives, titanium-based adhesives, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and β-keto acids Ester compounds, amino compounds, etc.

Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and International Publication No. 2011/080992 The compounds described in paragraphs 0063 to 0071, the compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264, International Publication No. 2014 /097594, the compound described in paragraph 0055. In addition, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP 2011-128358 A. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulae, Et represents an ethyl group.

[Chemical formula 29]

As other silane coupling agents, for example, vinyl trimethoxy silane, vinyl triethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-epoxy Propoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropoxy Propyl propyl triethoxy silane, p-styryl trimethoxy silane, 3-methacryloxy propyl methyl dimethoxy silane, 3-methacryloxy propyl trimethoxy silane , 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, N- 2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane , 3-Aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxy Silane, tris-(trimethoxysilylpropyl) isocyanurate, 3-ureapropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxy Silane, 3-isocyanate propyl triethoxy silane, 3-trimethoxysilyl propyl succinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

In addition, as the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and sulfide compounds described in paragraphs 0032 to 0043 of JP 2013-072935 can also be used. .

〔Aluminum series adhesive additives〕 As an aluminum-based adhesive agent, for example, tris(acetate ethyl acetate) aluminum, tris(acetacetone) aluminum, ethyl acetate diisopropyl aluminum, and the like can be cited.

The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the specific resin. By setting it as the above lower limit or more, the adhesiveness of the cured film after the curing process to the metal layer becomes better, and by setting it as the above upper limit value or less, the heat resistance and mechanical properties of the cured film after the curing process become better. There may be only one type of metal adhesion improver, or two or more types. When two or more types are used, the total of them is preferably in the above-mentioned range.

＜Other additives＞ The negative type curable composition of the present invention can be blended with various additives as required within the range where the effects of the present invention can be obtained, for example, sensitizers such as N-phenyldiethanolamine, dissolution promoters, chain transfer agents, interface Active agents, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the negative curable composition.

〔Sensitizer〕 The negative-type curable composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photo-radical polymerization initiator, etc., to produce effects such as electron transfer, energy transfer, and heat generation. Thereby, the thermal radical polymerization initiator and the photo radical polymerization initiator undergo chemical changes to decompose, and generate free radicals, acids, or bases. Examples of the sensitizer include sensitizers such as N-phenyldiethanolamine. In addition, benzophenone series, Michelone series, coumarin series, pyrazole azo series, anilino azo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series can also be used System, benzylidene system, oxacyanine system, pyrazolotriazole azo system, pyridone azo system, cyanine system, phenothionine system, pyrrolopyrazole azomethine system, pyrrolopyrazole azomethine system , Phthalocyanine series, benzopiperan series, indigo series and other compounds. For example, Michelone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2, 6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'- Bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminobenzene allylindanone, p-dimethylamino Benzylene indanone, 2-(p-dimethylaminophenyl biphenyl)-benzothiazole, 2-(p-dimethylaminophenyl vinylidene) benzothiazole, 2-(p-diphenyl) Methylaminophenyl vinylene) isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene) ) Acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-di Methylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl- 7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N -P-toluene diethanolamine, N-phenylethanolamine, 4-terminal benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole , 1-Phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyrene) benzoxazole, 2-(p-dimethylaminostyrene) benzo Thiazole, 2-(p-dimethylaminostyrene)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzyl Aniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc. In addition, as a sensitizer, a sensitizing dye can also be used. For the details of the sensitizing dye, reference can be made to the description in paragraphs 0161 to 0163 of JP 2016-027357 A, which is incorporated into this specification.

When the negative-type curable composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01-20% by mass, and 0.1-15% by mass relative to the total solid content of the negative-type curable composition of the present invention. It is more preferable, and 0.5 to 10% by mass is still more preferable. One kind of sensitizer may be used alone, or two or more kinds may be used at the same time.

〔Dissolution enhancer〕 Examples of the dissolution accelerator include polyhydroxy compounds and the like. By including the dissolution accelerator in the negative curable composition, for example, the developability can be improved. Examples of polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, 4,4',4"-ethylene triphenol (TrisP-HAP), TrisP-PA, TrisP-SA, TrisOCR- PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene tris-FR-CR, BisRS-26X, DML -MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML -MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above trade name, Honshu Chemical Industry Co. , Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above trade name, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tertiary butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-Diacetyloxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (Trade name, manufactured by Honshu Chemical Industry Co., Ltd.), but not limited to these.

When the negative-type curable composition of the present invention contains a dissolution accelerator, the content of the dissolution accelerator relative to the total solid content of the negative-type curable composition of the present invention is preferably 0.01-40% by mass, and 0.1-30% by mass It is more preferable, and 0.5 to 20% by mass is still more preferable. One kind of dissolution accelerator may be used alone, or two or more kinds may be used at the same time.

[Chain Transfer Agent] The negative curable composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined in, for example, pages 683-684 of the third edition of the Polymer Dictionary (Edited by The Society of Polymer Science (Japan), 2005). As the chain transfer agent, for example, a _{compound group having -SS-, -SO 2} -S-, -NO-, SH, PH, SiH, and GeH in the molecule can be used for RAFT (Reversible Addition Fragmentation Chain Transfer: Reversible Addition Fragmentation Chain Transfer). Addition, fragmentation, chain transfer) polymerization of dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compound with thiocarbonylthio group. These provide hydrogen to low-activity free radicals to generate free radicals, or after oxidation, they can generate free radicals by deprotonation. In particular, thiol compounds can be preferably used.

In addition, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used.

When the negative-type curable composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01-20 parts by mass relative to 100 parts by mass of the total solid content of the negative-type curable composition of the present invention, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is still more preferable. There may be only one type of chain transfer agent, or two or more types. When there are two or more chain transfer agents, it is preferable that the total of them is in the above-mentioned range.

又，界面活性劑亦能夠使用國際公開第2015/199219號的0159～0165段中記載之化合物。[Surfactant] From the viewpoint of further improving coatability, various surfactants can be added to the negative curable composition of the present invention. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. In addition, the following surfactants are also preferable. In the following formula, the parentheses representing the repeating unit of the main chain represent the content (mol %) of each repeating unit, and the parentheses representing the repeating unit of the side chain represent the repeating number of each repeating unit. [Chemical formula 30]

In addition, as the surfactant, the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.

When the negative curable composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass relative to the total solid content of the negative curable composition of the present invention, more preferably 0.005 to 1.0% by mass. There may be only one type of surfactant, or two or more types. When there are two or more surfactants, it is preferable that the sum total is in the above-mentioned range.

〔Higher fatty acid derivatives〕 In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide can be added to the negative-curing composition of the present invention, and it can be used in the drying process after coating. Partially on the surface of the negative-type curable composition.

In addition, the higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015/199219.

When the negative curable composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the negative curable composition of the present invention. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more higher fatty acid derivatives, it is preferable that the sum total is within the above-mentioned range.

＜Regarding restrictions on other contained substances＞ From the viewpoint of coating surface properties, the moisture content of the negative curable composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and more preferably less than 0.6% by mass.

From the viewpoint of insulation, the metal content of the negative curable composition of the present invention is preferably less than 5 mass ppm (parts per million), preferably less than 1 mass ppm, and less than 0.5 mass ppm. To be further preferred. Examples of metals include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total of these metals is preferably within the above-mentioned range.

In addition, as a method of reducing metal impurities accidentally contained in the negative-type curable composition of the present invention, the following method can be cited: as a raw material constituting the negative-type curable composition of the present invention, a raw material with a small metal content is selected , Filter the raw materials constituting the negative curable composition of the present invention, line the device with polytetrafluoroethylene or the like, and perform distillation under the condition of suppressing pollution as much as possible.

Considering the use as a semiconductor material, from the perspective of wiring corrosion, the negative curable composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm. ppm is more preferable. Among them, less than 5 mass ppm is preferable in the state of halogen ions, less than 1 mass ppm is more preferable, and less than 0.5 mass ppm is more preferable. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of the chlorine atom and the bromine atom or the chlorine ion and the bromine ion be in the above-mentioned range.

As the storage container of the negative curable composition of the present invention, a conventionally known storage container can be used. In addition, as a storage container, for the purpose of preventing impurities from mixing into the raw material or negative-curing composition, it is also better to use a multi-layer bottle with 6 kinds of 6-layer resins forming the inner wall of the container, and a bottle with 6 kinds of resins into a 7-layer structure. good. As such a container, for example, the container described in JP 2015-123351 A can be cited.

＜Use of negative type curable composition＞ The negative-type curable composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, or the like.

＜Preparation of negative curable composition＞ The negative curable composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and it can be performed by a conventionally known method.

In addition, for the purpose of removing foreign matter such as dust or particles in the negative curable composition, it is preferable to perform filtration using a filter. Regarding the filter pore size, for example, it may be 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be cleaned in advance with an organic solvent. In the filter filtration process, multiple filters can be used in parallel or in series. When multiple filters are used, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cyclic filtering. In addition, filtration may be performed after pressurization. When filtering by pressure, the applied pressure may be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. It is more preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using filters, it can also be used to remove impurities using adsorbent materials. It can also be combined with filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

(Cured film, laminate, semiconductor device, and manufacturing methods of these) Next, the cured film, the laminated body, the semiconductor device, and the manufacturing method thereof will be described.

The cured film of the present invention is formed by curing the negative curable composition of the present invention. The film thickness of the cured film of the present invention can be set to 0.5 μm or more, and can be set to 1 μm or more, for example. Moreover, as an upper limit, it can be 100 micrometers or less, and can also be 30 micrometers or less.

Two or more layers of the cured film of the present invention can be laminated, and 3 to 7 layers can be laminated as a laminated body. The layered product of the present invention includes two or more cured films, and it is preferable to include a metal layer between any of the above-mentioned cured films. For example, a laminated body including at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order can be cited as a preferable one. The first cured film and the second cured film are both cured films of the present invention. For example, the first cured film and the second cured film are both cured by curing the negative curable composition of the present invention. The aspect of the formed film is the better one. The negative-type curable composition of the present invention for forming the above-mentioned first cured film and the negative-type curable composition of the present invention for forming the above-mentioned second cured film may have the same composition or different compositions The composition. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a rewiring layer.

Examples of the field to which the cured film of the present invention can be applied include insulating films of semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition to this, a sealing film, a substrate material (a base film or a cover film of a flexible printed circuit board, an interlayer insulating film), or a case where a pattern is formed by etching an insulating film for actual mounting purposes as described above, etc. can be mentioned. For these uses, for example, you can refer to Science & Technology Co., Ltd. "High-functionalization and Application Technology of Polyimide" April 2008, Kakimoto Masaki/Supervisor, CMC Technical Library "Polyimide Materials The foundation and development of "Polyimine" issued in November 2011, Japan Polyimine and Aromatic Polymer Research Society/Edition "The latest polyimine basics and applications" NTS, August 2010, etc.

In addition, the cured film in the present invention can also be used for the production of offset printing plates and screen plates, the use of etching molded parts, the production of protective paints and dielectric layers in electronics, especially microelectronics, and the like.

The manufacturing method of the cured film of the present invention (hereinafter, also referred to simply as "the manufacturing method of the present invention".) preferably includes a film forming process of applying the negative curable composition of the present invention to a substrate to form a film. The method for producing a cured film of the present invention preferably includes the above-mentioned film formation process, an exposure process for exposing the film, and a development process for developing the film. Furthermore, it is more preferable that the method for producing a cured film of the present invention includes a heating process of heating the above-mentioned film. Specifically, the manufacturing process including the following (a) to (d) is also preferable. (A) A film forming process in which a negative type curable composition is applied to a substrate to form a film (negative type curable composition layer) (B) Exposure process for exposing the film after the film formation process (C) Development process for developing the exposed film (D) Heating process for heating the developed film By heating in the above heating process, the resin layer hardened by exposure can be further cured. In this heating process, for example, the thermal acid generator described above decomposes, and the generated acid promotes the crosslinking of the thermal crosslinking agent, thereby obtaining sufficient curability.

The manufacturing method of the laminated body of the preferable embodiment of this invention includes the manufacturing method of the cured film of this invention. The manufacturing method of the laminated body of this embodiment follows the above-mentioned manufacturing method of the cured film. After the cured film is formed, the process of (a) or the process of (a) to (c) or the process of (a) to (d) is performed again. Process. In particular, it is preferable to sequentially perform the above-mentioned processes a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). By layering the cured film in this way, a layered body can be formed. In the present invention, it is particularly preferable to provide a metal layer on the part where the cured film is provided, between the cured films, or both. In addition, in the production of the laminate, it is not necessary to repeat all the processes of (a) to (d). As described above, it can be performed multiple times at least (a), preferably (a) to (c) or (a) ~(d) Process to obtain a laminate of cured film.

<Film formation process (layer formation process)> The manufacturing method of the preferred embodiment of the present invention includes a film formation process (layer formation process) in which a negative curable composition is applied to a substrate to form a film (layered).

The type of substrate can be appropriately set according to the application. It can be used to make substrates for semiconductors such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, and reflective films. , Ni, Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, electrode plates of plasma display panels (PDP), etc., are not particularly limited. In the present invention, in particular, semiconductor manufacturing substrates are preferred, and silicon substrates and mold resin substrates are more preferred. In addition, as the base material, for example, a plate-shaped base material (substrate) is used.

In addition, when the negative-type curable composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes the base material.

As a method of applying the negative curable composition to the substrate, coating is preferred.

Specifically, as applicable methods, there can be exemplified dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, Slit coating method and inkjet method, etc. From the viewpoint of the uniformity of the thickness of the negative curable composition layer, the spin coating method, the slit coating method, the spray coating method, and the inkjet method are more preferable. By adjusting the appropriate solid content concentration or coating conditions according to the method, a resin layer with a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a round substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and as long as it is a rectangular substrate, the slit Coating method, spraying method, inkjet method, etc. are preferable. When using the spin coating method, for example, it can be applied at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds, and it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. In addition, in order to obtain a uniform film thickness, it is also possible to perform coating in combination with a plurality of rotation speeds. In addition, it is also possible to apply a method of transferring a coating film formed by applying the above-mentioned applying method on a pseudo support in advance to a substrate. Regarding the transfer method, in the present invention, the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592 can also be preferably used. .

＜Drying process＞ The manufacturing method of the present invention may further include a process of drying in order to remove the solvent after forming the above-mentioned film (negative curable composition layer), followed by a film forming process (layer forming process). The preferred drying temperature is 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes. When the amount of solvent in the negative curable composition solution is large, vacuum drying and heat drying can also be combined. A hot plate, a hot-air oven, etc. can be used for the heating and drying, and there is no particular limitation.

<Exposure Process> The manufacturing method of the present invention may include an exposure process of exposing the above-mentioned film (negative type curable composition layer). The exposure amount is not particularly limited as long as it can harden the negative-type curable composition. For example, in terms of exposure energy at a wavelength of 365 nm, 100 to 10,000 mJ/cm ² is preferable, and 200 to 8,000 mJ/cm ² For better.

The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

Regarding the exposure wavelength, if it is described in terms of the relationship with the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-ray (Wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm) , ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, etc., (7) secondary YAG laser Harmonic 532nm, third harmonic 355nm. For the negative-type curable composition of the present invention, exposure based on high-pressure mercury lamps is particularly preferred, and exposure based on i-rays is particularly preferred. In this way, particularly high exposure sensitivity can be obtained. In addition, from the viewpoints of operability and productivity, a wide (3 wavelengths of g, h, and i rays) light source for a high-pressure mercury lamp or a semiconductor laser of 405 nm is also preferable.

＜Development process＞ The manufacturing method of the present invention may include a development process of developing (developing the above-mentioned film) the exposed film (negative-type curable composition layer). By developing, the unexposed part (non-exposed part) is removed. The development method is not particularly limited as long as the desired pattern can be formed. For example, development methods such as coating, spraying, dipping, and ultrasonic can be used.

The development is performed using a developer. Regarding the developer, as long as the unexposed part (non-exposed part) can be removed, it can be used without particular limitation.

As the developer, it is preferable that the content of the organic solvent is 10% by mass or less with respect to the total mass of the developer, it is more preferable that the developer is 5% by mass or less, and the developer is 1% by mass or less. Best, the developer without organic solvent is particularly good. The developer in alkali development is more preferably an aqueous solution with a pH of 10-15. As the alkali compound contained in the developer in the alkali development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, metasilica Sodium, potassium metasilicate, ammonia or amine, etc. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, and quaternary ammonium hydroxide. , Tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc. Among them, metal-free alkali compounds are preferred, and ammonium compounds are more preferred. There may be only one kind of alkali compound, or two or more kinds. When there are two or more kinds of alkali compounds, it is preferable that the total of them is in the above-mentioned range.

In addition, a surfactant may be contained in the developer.

As the development time, 10 seconds to 5 minutes are preferred. The temperature of the developer during development is not particularly limited, and it can usually be performed at 20 to 40°C.

After the treatment with the developer, it can be further rinsed. It is better to rinse with a solvent different from the developer. For example, it can be rinsed with water. The rinsing time is preferably 5 seconds to 1 minute.

＜Heating process＞ The manufacturing method of the present invention preferably includes a process of heating the developed film (heating process). It is preferable to include a heating process after the film forming process (layer forming process), drying process, and developing process. In the heating process, for example, the crosslinking of the unreacted radical crosslinking agent, the crosslinking of the unreacted thermal crosslinking agent, etc. can be performed. As the heating temperature (maximum heating temperature) of the layer in the heating process, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is even more preferred, 150°C or higher is even more preferred, and 160°C or higher is even further Preferably, 170°C or higher is even more preferable. As the upper limit, 500°C or less is preferred, 450°C or less is more preferred, 350°C or less is more preferred, 250°C or less is even more preferred, and 220°C or less is still more preferred.

From the temperature at the start of heating to the maximum heating temperature, heating is preferably performed at a temperature increase rate of 1-12°C/min, more preferably 2-10°C/min, and still more preferably 3-10°C/min. By setting the temperature increase rate to 1°C/min or more, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C/min or less, the residual stress of the cured film can be alleviated.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and more preferably 25°C to 120°C. The temperature at the beginning of heating refers to the temperature at the beginning of the process when heating to the highest heating temperature. For example, when the negative-type curable composition is applied to the substrate and then dried, the temperature of the dried film (layer) is, for example, 30 to 200 lower than the boiling point of the solvent contained in the negative-type curable composition. It is preferable that the temperature of °C start to increase gradually.

The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and more preferably 30 to 240 minutes.

In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between the layers of the cured film, heating at a heating temperature of 180°C to 320°C is preferable, and heating at 180°C to 260°C is more preferable. The reason for this is not certain, but it is thought that by setting the temperature at this temperature, the ethynyl groups of the specific resins between the layers undergo crosslinking reaction with each other.

Heating can be carried out in stages. As an example, a pre-treatment process can be performed at 3°C/min from 25°C to 180°C and holding at 180°C for 60 minutes, and 2°C/min from 180°C to 200°C and holding at 200°C for 120 minutes. As the heating temperature of the pretreatment process, 100-200°C is preferred, 110-190°C is more preferred, and 120-185°C is even more preferred. In this pre-treatment process, as described in the specification of US Patent No. 9159547, it is also preferable to perform treatment while irradiating ultraviolet rays. Through this kind of pre-treatment process, the characteristics of the film can be improved. The pre-treatment process can be carried out in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pre-treatment may be a two-stage or more process, for example, the pre-treatment process 1 may be performed in the range of 100-150°C, and then the pre-treatment process 2 may be performed in the range of 150-200°C.

Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/min.

From the viewpoint of preventing decomposition of the specific resin, it is preferable to perform the heating process in a low oxygen concentration environment by performing the heating process under a vacuum in which an inert gas such as nitrogen, helium, and argon flows. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

＜Metal layer forming process＞ The manufacturing method of the present invention preferably includes a metal layer forming process of forming a metal layer on the surface of the developed film (negative type curable composition layer).

The metal layer is not particularly limited, and existing metal types can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is still more preferable.

The method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, and Japanese Patent Application Publication No. 2004-101850 can be used. For example, methods such as photolithography, peeling, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating can be cited.

As for the thickness of the metal layer, at the thickest part, 0.1-50 μm is preferable, and 1-10 μm is more preferable.

＜Layer Process＞ Preferably, the manufacturing method of the present invention further includes a build-up process.

The build-up process includes on the surface of the cured film (resin layer) or the metal layer, and then sequentially perform one of (a) film formation process (layer formation process), (b) exposure process, (c) development process, and (d) heating process. A series of manufacturing processes. Among them, it may be a mode in which only the film formation process of (a) is repeated. In addition, it can also be set as (d) a state in which the heating process is performed uniformly at the end or in the middle of the buildup. That is, it can also be set as a mode in which the processes of (a) to (c) are repeated a predetermined number of times, and then the heating of (d) is performed to uniformly harden the laminated negative curable composition layer. In addition, (c) the development process may include (e) the metal layer forming process. In this case, the heating of (d) may be performed each time, or the heating of (d) may be performed uniformly after a predetermined number of laminations. There is no doubt that the above-mentioned drying process and heating process can also be appropriately included in the build-up process.

When the build-up process is further performed after the build-up process, the surface activation treatment process may be further performed after the above-mentioned heating process, after the above-mentioned exposure process, or after the above-mentioned metal layer formation process. As the surface activation treatment, plasma treatment can be exemplified.

The above-mentioned layering process is preferably carried out 2 to 5 times, and it is more preferable to carry out 3 to 5 times.

For example, resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer are preferably three or more and seven or less resin layers, and more preferably three or more and five or less resin layers.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the negative-type curable composition in such a manner that the metal layer is further covered after the metal layer is provided. Specifically, it can be mentioned that (a) film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, (d) heating process are repeated in sequence, or (a) is repeated in sequence Film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, and (d) heating process is uniformly set at the end or in the middle. By alternately laminating the negative-type curable composition layer (resin layer) and the metal layer forming process, it is possible to alternately laminate the negative-type curable composition layer (resin layer) and the metal layer.

The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the negative-type curable composition of the present invention is used to form an interlayer insulating film for a rewiring layer, refer to the description in paragraphs 0213 to 0218 of JP 2016-027357 A and the description in FIG. 1 , These contents are incorporated into this manual. [Example]

Hereinafter, the benzene invention will be described in further detail with examples. The materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are quality standards.

＜Synthesis example 1＞ 〔A-1: Using oxydiphthalic dianhydride, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1,3-bis(3-aminopropyl)tetra Synthesis of alkali-soluble polyimide A-1 of methyldisiloxane and 2-isocyanatoethyl methacrylate] In a drying reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser and an internal thermometer, 65.56g (179mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was removed while removing water. ) And 1,3-bis(3-aminopropyl)tetramethyldisiloxane 2.48g (10mmol) are dissolved in 300g of N-methylpyrrolidone (NMP). Next, 62.04 g (200 mmol) of oxydiphthalic dianhydride was added, and the mixture was stirred at a temperature of 40°C for 2 hours. Next, 50 mL of toluene and 2.18 g (10 mmol) of 3-aminophenol were added, and the mixture was stirred at 40°C for 2 hours. After stirring, nitrogen was flowed at a flow rate of 200 ml/min, the temperature was raised to 180°C, and stirring was carried out for 6 hours. After cooling the above-mentioned reaction liquid to 25°C, 0.005 g of p-methoxyphenol was added and dissolved. 24.82 g (160 mmol) of 2-isocyanatoethyl methacrylate was added dropwise to this solution, and after stirring at 25°C for 2 hours, it was further stirred at 60°C for 3 hours. This was cooled to 25°C, 10 g of acetic acid was added, and the mixture was stirred at 25°C for 1 hour. After stirring, it was precipitated in 2 liters of water/methanol=75/25 (volume ratio), and stirred at a speed of 2,000 rpm for 30 minutes. The precipitated polyimide resin was collected by filtration, and after washing with 1.5 liters of water, the filtrate was mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again. The obtained polyimide was dried under reduced pressure at 40°C for 1 day to obtain A-1.

＜Synthesis example 2＞ 〔A-2: Using oxydiphthalic dianhydride, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,3-bis(3-aminopropyl)tetramethyl Synthesis of alkali-soluble polyimide A-2 of disiloxane and 2-isocyanatoethyl methacrylate] In the synthesis of A-1, the same molar amount of 2,2-bis(3-amino-4-hydroxyphenyl)propane was used instead of 2,2-bis(3-amino-4-hydroxyphenyl) ) Hexafluoropropane, except for this, the alkali-soluble polyimide A-2 was synthesized in the same way as the synthesis of A-1.

＜Synthesis example 3＞ 〔A-3: Using the alkali solubility of oxydiphthalic dianhydride, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2-isocyanatoethyl methacrylate Synthesis of polyimide A-3] In the synthesis of A-1, 1,3-bis(3-aminopropyl)tetramethyldisiloxane was not used and 2,2-bis(3-amino-4-hydroxyphenyl)hexa Except that the amount of fluoropropane used was 69.22 g (189 mmol), the alkali-soluble polyimide A-3 was synthesized in the same manner as in the synthesis of A-1.

＜Synthesis example 4＞ 〔A-4: Using oxydiphthalic dianhydride, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 1,3-bis(3-aminopropyl)tetra Synthesis of alkali-soluble polyimide A-4 of methyldisiloxane] In the synthesis of A-1, the addition of 2-isocyanatoethyl methacrylate was not carried out. Except for this, the alkali-soluble polyimide A-4 was synthesized in the same way as the synthesis of A-1. .

＜Synthesis example 5＞ 〔A-5: Using oxydiphthalic dianhydride, 2,5-dimercapto-p-diamine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane and methacrylic acid 2 -Synthesis of alkali-soluble polyimide A-5 of ethyl isocyanate] In the synthesis of A-1, the same molar amount of 2,5-dimercapto-p-this diamine was used instead of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. In addition, In the same way as the synthesis of A-1, alkali-soluble polyimide A-5 was synthesized.

<Examples and Comparative Examples> In each example, the components described in the following Tables 1 to 3 were mixed to obtain each negative curable composition. In addition, in each comparative example, the components described in the following Table 3 were mixed to obtain each comparative composition. Specifically, the content of the components described in Tables 1 to 3 is set to the amount described in "parts by mass" of Tables 1 to 3. In addition, in each composition, the content of the solvent was such that the solid content concentration of the composition became the value described in Tables 1 to 3. The description in the “metal concentration” column in Tables 1 to 3 indicates the metal content (mass ppm) relative to the total mass of the composition. The obtained negative-type curable composition and the comparative composition were filtered under pressure through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm. In addition, in Tables 1 to 3, the description of "-" indicates that the composition does not contain the component.

[Table 1] Example 1 2 3 4 5 6 7 8 9 10 composition Alkali-soluble polyimide species A-1 A-1 A-1 A-2 A-3 A-4 A-5 A-1 A-1 A-1 Mass parts 54 54 54 54 54 54 54 54 54 54 Free radical crosslinker species B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Mass parts 3 3 3 3 3 3 3 3 3 3 species B-3 B-4 B-3 B-3 B-3 B-3 B-3 B-3 B-3 B-3 Mass parts 28 28 28 28 28 28 28 28 28 28 Light free radical generator species C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-2 Mass parts 5 5 5 5 5 5 5 5 5 5 Thermal crosslinking agent species D-1 D-2 D-2 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Mass parts 9 9 9 9 9 9 9 9 9 9 Thermal acid generator species E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 Mass parts 3 3 3 3 3 3 3 3 3 3 Silane coupling agent species F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 Mass parts 1 1 1 1 1 1 1 1 1 1 Polymerization inhibitor species G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 Mass parts 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 additive species H-1 H-1 H-1 H-1 H-1 H-1 H-1 - H-1 H-1 Mass parts 1 1 1 1 1 1 1 - 1 1 Solvent species I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Ratio in solvent 80 80 80 80 80 80 80 80 50 80 species I-4 I-4 I-4 I-4 I-4 I-4 I-4 I-4 I-4 I-4 Ratio in solvent 20 20 20 20 20 20 20 20 50 20 Solid content concentration 42 42 42 42 42 42 42 42 42 42 Metal concentration (ppm) 1 1 1 1 1 1 1 1 1 1 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 Hardening temperature (℃) 200 200 200 200 200 200 200 200 200 200 Hardening time (min) 120 120 120 120 120 120 120 120 120 120 Evaluation results Evaluation of elongation at break A B A B B B A A B A Solvent resistance evaluation A A A A A A A A A A Adhesion evaluation A A A A A A A B A A

[Table 2] Example 11 12 13 14 15 16 17 18 19 composition Alkali-soluble polyimide species A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 Mass parts 54 54 54 54 54 54 54 54 54 Free radical crosslinker species B-1 - B-1 B-1 B-1 B-1 B-1 B-1 B-1 Mass parts 3 - 3 3 3 3 3 3 3 species B-3 B-3 B-3 B-3 B-3 B-3 B-3 B-3 B-3 Mass parts 28 31 28 28 28 28 28 28 28 Light free radical generator species C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Mass parts 5 5 5 5 5 5 5 5 5 Thermal crosslinking agent species D-3 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Mass parts 9 9 9 9 9 9 9 9 9 Thermal acid generator species E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 Mass parts 3 3 3 3 3 3 3 3 3 Silane coupling agent species F-1 F-1 F-1 F-1 F-1 F-2 F-1 F-1 F-1 Mass parts 1 1 1 1 1 1 1 1 1 Polymerization inhibitor species G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 Mass parts 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 additive species H-1 H-1 H-1 H-1 H-1 H-1 H-2 H-1 H-1 Mass parts 1 1 1 1 1 1 1 1 1 Solvent species I-1 I-1 I-1 I-1 I-2 I-1 I-1 I-3 I-1 Ratio in solvent 80 80 80 80 80 80 80 80 80 species I-4 I-4 I-4 I-4 I-4 I-4 I-4 I-5 I-4 Ratio in solvent 20 20 20 20 20 20 20 20 20 Solid content concentration 42 42 42 42 42 42 42 42 42 Metal concentration (ppm) 1 1 1 1 1 1 1 1 1 Process Film thickness (μm) 20 20 20 20 20 20 20 20 40 Hardening temperature (℃) 200 200 200 180 200 200 200 200 200 Hardening time (min) 120 120 120 120 120 120 120 120 120 Evaluation results Evaluation of elongation at break A B A A A A A A B Solvent resistance evaluation A A A A A A A A A Adhesion evaluation A B A A B A B A A

[table 3] Example Comparative example 20 twenty one twenty two twenty three twenty four 25 1 2 3 composition Alkali-soluble polyimide species A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 Mass parts 54 54 54 54 54 54 54 54 54 Free radical crosslinker species B-1 B-1 B-1 B-2 B-1 B-1 B-1 B-1 B-1 Mass parts 3 3 3 3 3 3 3 3 3 species B-5 B-6 B-7 B-3 B-8 B-3 B-4 B-9 B-10 Mass parts 28 28 28 28 28 14 28 28 28 Light free radical generator species C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Mass parts 5 5 5 5 5 5 5 5 5 Thermal crosslinking agent species D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Mass parts 9 9 9 9 9 9 9 9 9 Thermal acid generator species E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 Mass parts 3 3 3 3 3 3 3 3 3 Silane coupling agent species F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 Mass parts 1 1 1 1 1 1 1 1 1 Polymerization inhibitor species G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 G-1 Mass parts 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 additive species H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 Mass parts 1 1 1 1 1 1 1 1 1 species - - - - - H-3 - - - Mass parts - - - - - 14 - - - Solvent species I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Ratio in solvent 80 80 80 80 80 80 80 80 80 species I-4 I-4 I-4 I-4 I-4 I-4 I-4 I-4 I-4 Ratio in solvent 20 20 20 20 20 20 20 20 20 Solid content concentration 42 42 42 42 42 42 42 42 42 Metal concentration (ppm) 1 1 1 1 1 1 1 1 1 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 Hardening temperature (℃) 200 200 200 200 200 200 200 200 200 Hardening time (min) 120 120 120 120 120 120 120 120 120 Evaluation results Evaluation of elongation at break B A A A A A C C C Solvent resistance evaluation A A A A A A B A A Adhesion evaluation B A A A A B C B B

The details of each component described in Table 1 to Table 3 are as follows.

〔Alkali-soluble polyimide〕 ・A-1～A-5: A-1～A-5 synthesized in the above

〔Free radical crosslinking agent〕 ・B-1: Dineopentaerythritol hexaacrylate ・B-2: Neopentylerythritol tetramethacrylate ・B-3: Tetraethylene glycol dimethacrylate ・B-4: LIGHT ESTER BP-6EM (manufactured by KYOEISHA CHEMICAL Co., LTD.) ・B-5: 1,8-octanediol dimethacrylate ・B-6: 1,10-decanediol dimethacrylate ・B-7: 1,12-Dodecanediol dimethacrylate ・B-8: Hexaethylene glycol dimethacrylate ・B-9: 1,6-hexanediol dimethacrylate ・B-10: Diethylene glycol dimethacrylate The above-mentioned B-1 and the above-mentioned B-2 have 6 or 4 polymerized groups, which do not correspond to a specific bifunctional crosslinking agent. The above-mentioned B-3 does not have a cyclic structure based on a covalent bond and the distance between the polymer groups is 15 atoms, so it corresponds to a specific bifunctional crosslinking agent. The above-mentioned B-4 has a cyclic structure (benzene ring structure) based on a covalent bond at a site other than the polymerizing group, and therefore does not correspond to a specific bifunctional crosslinking agent. The above-mentioned B-5, the above-mentioned B-6, the above-mentioned B-7, and the above-mentioned B-8 do not have a cyclic structure based on a covalent bond and the distance between the polymer groups is 12 atoms, 14 atoms, 16 atoms, and 21 atoms, respectively. , So it meets the specific bifunctional crosslinking agent. The above-mentioned B-9 and the above-mentioned B-10 do not correspond to the specific bifunctional crosslinking agent because the distance between the polymer groups is 10 atoms and 9 atoms, respectively.

〔Light radical generator〕 ・C-1: ADEKA NCI-930 (manufactured by ADEKA CORPORATION) ・C-2: Omnirad 819 (manufactured by IGM Resins)

〔Heat crosslinking agent〕 ・D-1: NIKALAC MX-270 (manufactured by SANWA CHEMICAL CO., LTD) ・D-2: DENACOL EX-821 (manufactured by Nagase ChemteX Corporation) ・D-3: HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) The above D-1 has a covalent bond-based cyclic structure (glycolurea structure) at a position other than the polymerizing group and has 4 methoxymethyl groups as the polymerizing group-containing group, so it is not Meet the specific bifunctional crosslinking agent. The above-mentioned D-2 does not have a cyclic structure based on a covalent bond at a site other than a polymerized group, and the distance between the polymerized groups is 15 atoms, and therefore conforms to a specific bifunctional crosslinking agent. The above-mentioned D-3 has a covalent bond-based cyclic structure (benzene ring structure) and 6 methoxymethyl groups as a group containing a polymerized group at a position other than the polymerized group, so it does not meet the specific requirements. 2-functional crosslinking agent.

〔Hot acid generator〕 ・E-1: Isopropyl p-toluenesulfonate

〔Silane Coupling Agent〕 ・F-1: IM-1000 (manufactured by JX Nippon Mining & Metals Corporation) ・F-2: KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.)

〔Polymerization inhibitor〕 ・G-1: 4-Methoxy-1-naphthol

〔additive〕 ・H-1: 1,3-Dibutylthiourea ・H-2: N-Butylbenzenesulfonamide ・H-3: 4,4’,4’’-ethylene triphenol (manufactured by Honshu Chemical Industry Co., Ltd.)

〔Solvent〕 ・I-1: γ-Butyrolactone ・I-2: ε-Caprolactone ・I-3: N-Methyl-2-pyrrolidone ・I-4: Dimethyl sulfide ・I-5: Ethyl lactate In Tables 1 to 3, the description in the “ratio in solvent” column indicates the content (mass %) of each solvent with respect to the total mass of the solvent.

<Evaluation> [Elongation at break] In each of the Examples and Comparative Examples except Example 19, each negative curable composition or comparative composition was applied in a layered form by a spin coating method (coating ) On the silicon wafer, thereby forming a curable resin composition layer. In Example 19, the negative-type curable composition was applied (coated) on the silicon wafer in a layered form by the slit coating method, thereby forming a composition layer. In each of the Examples and Comparative Examples, the silicon wafer to which the obtained composition layer was applied was dried on a hot plate at 80°C for 5 minutes, thereby forming the descriptions in Table 1 to Table 3 on the silicon wafer The thickness of the curable resin composition layer. Using a stepper (Nikon NSR 2005 i9C), the entire surface of the curable resin composition layer on the silicon wafer was exposed with an exposure energy of ^{500 mJ/cm 2.} After the exposure, it was heated at 100°C for 5 minutes. The above-mentioned heated curable resin composition layer (resin layer) was heated in a nitrogen atmosphere at a temperature increase rate of 10°C/min to reach the temperature of the "curing temperature (°C)" in Tables 1 to 3, and then the The temperature was maintained for the time described in the "hardening time (min)" in Tables 1 to 3. The cured resin layer was immersed in a 4.9% hydrofluoric acid aqueous solution, and the resin layer was peeled from the silicon wafer to obtain a resin film 1.

Regarding the elongation at break of the resin film 1, using a tensile testing machine (TENSILON), the crosshead speed was set to 300 mm/min, the sample width was set to 10 mm, and the sample length was set to 50 mm. The elongation at break was measured in accordance with JIS-K6251:2017 under an environment of 25°C and 65% relative humidity (RH). The elongation at break is given by E _b (%) = (L _b -L ₀ )/L ₀ ×100 (E _b : elongation at the time of cutting, L ₀ : length of the test piece before the test, L _b : test piece The length of the test piece when it has been cut) is calculated. The elongation at break in the longitudinal direction was measured 5 times, and the arithmetic mean was used as the index value. The evaluation was performed in accordance with the following evaluation criteria. The evaluation results are described in the "Elongation at Break" column of Tables 1 to 3. It can be said that the larger the above index value, the more excellent the elongation at break of the cured film obtained. -Evaluation criteria-A: The above index value exceeds 60%. B: The above index value exceeds 40% and 60% or less. C: The above index value is 40% or less.

[Solvent resistance] In each of the examples and comparative examples except Example 19, each negative curable composition or comparative composition was spin-coated on a silicon wafer at 1,000 rpm and applied in a layered form (Coating), thereby forming a curable resin composition layer. In Example 19, the negative-type curable composition was applied (coated) on the silicon wafer in a layered form by the slit coating method, thereby forming a composition layer. In each of the Examples and Comparative Examples, the silicon wafer to which the obtained composition layer was applied was dried on a hot plate at 80°C for 5 minutes, thereby forming the descriptions in Table 1 to Table 3 on the silicon wafer The thickness of the curable resin composition layer. Using a stepper (Nikon NSR 2005 i9C), the entire surface of the curable resin composition layer on the silicon wafer was exposed with an exposure energy of ^{500 mJ/cm 2.} After the exposure, it was heated at 100°C for 5 minutes. The curable resin composition layer (resin layer) after the above exposure was heated in a nitrogen atmosphere at a temperature increase rate of 10°C/min to reach the temperature of the "curing temperature (°C)" in Tables 1 to 3, and then the The temperature was maintained for the time described in the "curing time (min)" of Tables 1 to 3, thereby obtaining a cured film. The silicon wafer with the cured film formed above was immersed in N-methyl-2-pyrrolidone for 3 hours, washed with isopropanol, and then air-dried. The air-dried cured film was visually observed for cracks, and the solvent resistance was evaluated in accordance with the following evaluation criteria. The evaluation results are described in the "solvent resistance" column of Tables 1 to 3. It can be said that the less likely to generate cracks, the better the solvent resistance of the cured film obtained. -Evaluation Criteria- A: No cracks were found on the entire surface of the wafer. B: A crack was found in at least a part of the wafer.

[Adhesion] In each of the Examples and Comparative Examples except Example 19, each negative curable composition or comparative composition was applied (coated) to a copper substrate in a layered form by a spin coating method. As a result, a curable resin composition layer was formed. In Example 19, the negative-type curable composition was applied (coated) in a layered form on the copper substrate by the slit coating method, thereby forming a composition layer. In each of the Examples and Comparative Examples, the copper substrate to which the obtained composition layer was applied was dried on a hot plate at 80°C for 5 minutes, thereby forming the thickness described in Table 1 to Table 3 on the copper substrate The curable resin composition layer. A stepper (Nikon NSR 2005 i9C) was used to expose the curable resin composition layer on the copper substrate at an exposure energy of ^{500mJ/cm 2 using a mask with a 100μm square non-masked part.} After the exposure, it was heated at 100°C for 5 minutes. After the above heating, it was developed in a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 5 minutes and rinsed with pure water for 20 seconds, thereby obtaining a 100 μm square resin layer. Furthermore, in a nitrogen atmosphere, the temperature was increased at a temperature increase rate of 10°C/min, and after reaching the temperature of the "hardening temperature (°C)" in Tables 1 to 3, the "hardening time (min)" in Tables 1 to 3 was maintained. The time recorded in.

In an environment of 25° C. and 65% relative humidity (RH), the shear force of a 100 μm square resin layer on the copper substrate was measured with an adhesion tester (manufactured by XYZTEC Corporation, CondorSigma). The greater the shear force, the greater the adhesion force for better results. The evaluation was performed in accordance with the following evaluation criteria. The evaluation results are described in the "adhesion" column of Tables 1 to 3. -Evaluation criteria- A: The shear force exceeds 40gf. B: The shear force exceeds 25 gf and is 40 gf or less. C: Shear force is 25 gf or less. Among them, 1gf is 9.80665×10 ^-3 N (Newton).

From the above results, it can be seen that the alkali-soluble polyimide according to the present invention, a photopolymerization initiator, does not have a cyclic structure based on a covalent bond at positions other than the polymerized group, and the distance between the polymerized groups is 12 A negative curable composition of a bifunctional crosslinking agent of more than atoms can obtain a cured film with excellent elongation at break. The negative curable composition of Comparative Example 1 to Comparative Example 3 does not contain bifunctional crosslinks that do not have a cyclic structure based on covalent bonds at positions other than polymerized groups and the distance between polymerized groups is 12 atoms or more Agent. It can be seen that the elongation at break of the cured film obtained from the negative curable composition of Comparative Example 1 to Comparative Example 3 is poor.

<Example 101> The negative curable composition used in Example 1 was applied to the surface of the copper thin layer of the resin substrate with the copper thin layer formed on the surface by the spin coating method, and dried at 80°C for 5 minutes, After forming a negative curable composition layer with a film thickness of 20 μm, exposure was performed using a stepper (manufactured by Nikon Corporation, NSR1505 i6). Through a mask (a binary mask with a pattern of 1:1 lines and spaces and a line width of 10 μm), exposure was performed at a wavelength of 365 nm. After the exposure, it was heated at 100°C for 5 minutes. After the above heating, it was developed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 5 minutes, and rinsed with pure water for 20 seconds, thereby obtaining a layer pattern. Next, the temperature was raised at a temperature increase rate of 10° C./min under a nitrogen atmosphere, and after reaching 200° C., the temperature was maintained at 200° C. for 120 minutes, thereby forming an interlayer insulating film for a rewiring layer. The interlayer insulating film for the rewiring layer has excellent insulating properties. In addition, as a result of fabricating semiconductor devices using these interlayer insulating films for rewiring layers, normal operation was confirmed.

no.

Claims (19)

A negative type hardening composition, which contains: Alkali-soluble polyimide; Photopolymerization initiator; and The bifunctional crosslinking agent does not have a cyclic structure based on a covalent bond at a site other than the polymerized group, and the distance between the polymerized groups is 12 atoms or more. The negative-type curable composition according to claim 1, wherein The aforementioned bifunctional crosslinking agent includes a polyoxyalkylene group. The negative-type curable composition as described in claim 1 or 2, wherein The aforementioned bifunctional crosslinking agent includes a compound that causes a polymerization reaction by the photosensitivity of the aforementioned photopolymerization initiator. The negative-type curable composition as described in claim 1 or 2, wherein The aforementioned bifunctional crosslinking agent includes a thermal crosslinking agent. The negative-type curable composition as described in claim 1 or 2, wherein The aforementioned alkali-soluble polyimide has a fluorine atom. The negative-type curable composition as described in claim 1 or 2, wherein The aforementioned alkali-soluble polyimide has a silicon atom. The negative-type curable composition as described in claim 1 or 2, wherein The aforementioned alkali-soluble polyimide has an ethylenically unsaturated bond. The negative-type curable composition as described in claim 1 or 2, wherein The aforementioned alkali-soluble polyimide has a phenolic hydroxyl group. The negative curable composition according to claim 1 or claim 2, which further comprises at least one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure. The negative-type curable composition as described in claim 1 or 2, wherein The aforementioned photopolymerization initiator is an oxime compound. The negative curable composition according to claim 1 or claim 2, which further comprises at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent. The negative curable composition according to claim 1 or claim 2, which further contains a compound having 3 to 6 ethylenically unsaturated bonds. The negative-type curable composition according to claim 1 or claim 2, which is used to form an interlayer insulating film for a rewiring layer. A cured film formed by curing the negative-type curable composition according to any one of Claims 1 to 13. A laminate comprising two or more layers of the cured film according to claim 14, and a metal layer is included between any of the cured films. A method for manufacturing a cured film, which includes a film forming process of applying the negative curable composition as described in any one of claims 1 to 13 to a substrate to form a film. The method for producing a cured film according to claim 16, which includes an exposure process for exposing the film and a development process for developing the film. The method for producing a cured film according to claim 16 or claim 17, which includes a heating process of heating the aforementioned film at 50°C to 450°C. A semiconductor device comprising the cured film according to claim 14 or the laminated body according to claim 15.