Photosensitive resin composition

Abstract

To provide a photosensitive resin composition which enables development with an alkaline aqueous solution at room temperature within a short time and allows formation of a cured product having superior linear thermal expansion coefficient, glass transition temperature, and elongation at break even at a low curing temperature.SOLUTION: This photosensitive resin composition contains the following component (A): a polyimide polymer having a structure derived from a tetracarboxylic dianhydride having an ether structure or an ester structure, and a structure derived from a diamine having a hydroxy structure, wherein a part or all of the hydroxy structure is modified by a structure derived from an epoxy compound having an ethylenically unsaturated bond.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, and further to a photosensitive film, a semiconductor package substrate, a semiconductor device, and a method for producing a semiconductor package substrate, which are obtained using the photosensitive resin composition. [Background technology]

[0002] Conventionally, polyimide resins and the like, which have excellent heat resistance, insulating properties, mechanical properties, etc., have been used for surface protection films and interlayer insulating films of semiconductor elements. In addition, since polyimide resins and the like have low solubility in solvents, they are used in the form of polyimide precursors in photosensitive resin compositions, and after forming an insulating layer or the like, the polyimide precursor is cyclized to produce polyimide, and an insulating layer is then formed.

[0003] For example, Patent Document 1 describes a photosensitive polyimide precursor having a skeleton derived from 4,4'-oxydiphthalic dianhydride and a skeleton derived from 4,4'-diaminodiphenyl ether, and a photosensitive polyimide precursor having a skeleton derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride and a skeleton derived from 4,4'-diaminodiphenyl ether. Patent Document 2 also proposes a silicone-modified polyimide resin. Furthermore, as a polyimide resin that can be developed with an alkaline aqueous solution, Patent Document 3 describes a negative-type photosensitive resin composition containing a polyimide resin of a specific structure, an anion regenerator, and a photoacid generator. Patent Document 4 describes a negative-type photosensitive polyimide composition containing a photoradical generator and a solvent-soluble polyimide that exhibits negative photosensitivity in the presence of the photoradical generator. Patent Document 5 describes an alkali negative-developing photosensitive resin composition containing a polyimide precursor soluble in an alkaline aqueous solution and having an acid functional group in the molecular chain, a photosensitizer, and a silicon compound having a reactive unsaturated functional group and an alkoxy group or an acyloxy group. Patent Document 6 describes a negative-type photosensitive resin composition containing a polyamic acid and a photobase generator of a specific structure. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6419383 [Patent Document 2] Patent No. 3646947 [Patent Document 3] Patent No. 5538779 [Patent Document 4] International Publication No. 2002 / 023276 [Patent Document 5] Japanese Patent Application Laid-Open No. 2001-281859 [Patent Document 6] Japanese Patent Application Laid-Open No. 2009-019113 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, for applications such as 5G communications, the number of layers used for rewiring semiconductor packages has increased from the conventional two to four or even five layers or more. Accordingly, there is a growing demand for cured products with a low coefficient of linear thermal expansion (CTE) to prevent warping of the laminated substrate, and cured products with high elongation at break to increase the mechanical strength of the package itself. Furthermore, to ensure the heat resistance of the laminated substrate, the cured products must also have a high glass transition temperature.

[0006] On the other hand, if a polyimide precursor such as polyamic acid is used in a photosensitive resin composition and then an insulating layer is formed, followed by cyclization of the polyimide precursor, a high-temperature curing reaction is required to imidize the polyimide precursor, which may adversely affect the packaged semiconductor chip. Furthermore, the imidization reaction after the insulating layer is formed is difficult to proceed because the water generated by the imidization reaction is difficult to remove. Since some polyamic acid structures remain even after the curing reaction, the physical properties of the cured product may deteriorate. Therefore, a polyimide resin that is soluble in organic solvents is desirable. Using a polyimide resin rather than a polyimide precursor in a photosensitive resin composition allows for a lower curing temperature, which is advantageous from the perspective of suppressing warpage of the laminate substrate.

[0007] Furthermore, from the viewpoint of safety regarding the volatilization of organic solvents and prevention of environmental pollution, there is also a demand for a photosensitive resin composition that can be developed at room temperature in a short time using an alkaline aqueous solution as a developer instead of an organic solvent during lithography.

[0008] The photosensitive resin compositions described in Patent Documents 1 to 6 do not satisfy the above requirements. The photosensitive resin composition described in Patent Document 1 uses a polyimide precursor and an organic solvent as a developer. The polyimide resin described in Patent Document 2 is not photosensitive, and a separate photoresist is required for pattern formation. The photosensitive resin composition described in Patent Document 3 can be developed with an alkaline aqueous solution, but the development takes a long time, resulting in reduced productivity. The photosensitive resin composition described in Patent Document 4 can also be developed with an alkaline aqueous solution, but requires heating to approximately 40°C during development. Alkaline aqueous solutions at high temperatures are extremely dangerous, so it is desirable to avoid them in industrial processes. The photosensitive resin composition described in Patent Document 5 does not mention heating when developing with an alkaline aqueous solution, but it uses a polyimide precursor and therefore requires high-temperature curing. Patent Document 6 also uses a polyimide precursor, and although the addition of a photobase generator has been investigated to lower the curing temperature, the curing temperature is 200°C, which is not sufficiently low.

[0009] The present invention has been made in view of the above-mentioned problems, and aims to provide a photosensitive resin composition that can be developed with an alkaline aqueous solution at room temperature in a short time and that can give a cured product that exhibits an excellent linear thermal expansion coefficient, glass transition temperature, and elongation at break at a low curing temperature, as well as a photosensitive film, a semiconductor package substrate, a semiconductor device, and a method for producing a semiconductor package substrate that use the same. [Means for solving the problem]

[0010] As a result of intensive investigations, the present inventors have found that the above-mentioned problems can be solved by using a photosensitive resin composition containing a polyimide polymer having a structure derived from a tetracarboxylic dianhydride having an ether structure or an ester structure and a structure derived from a diamine having a hydroxy structure, in which some or all of the hydroxy structures have been modified with a structure derived from an epoxy compound having an ethylenically unsaturated bond, and have thus completed the present invention.

[0011] That is, the present invention includes the following. [1] (A) A polyimide polymer having a structure derived from a tetracarboxylic dianhydride having an ether structure or an ester structure and a structure derived from a diamine having a hydroxy structure, in which a part or all of the hydroxy structures are modified with a structure derived from an epoxy compound having an ethylenically unsaturated bond; A photosensitive resin composition comprising: [2] The photosensitive resin composition according to [1], which is a negative type. [3] The photosensitive resin composition according to [1] or [2], wherein the structure derived from the tetracarboxylic dianhydride in the component (A) has an ether structure. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the structure derived from the tetracarboxylic dianhydride in the component (A) has an ester structure. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the epoxy compound having an ethylenically unsaturated bond in the component (A) is glycidyl (meth)acrylate. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the hydroxy structure in the component (A) is a hydroxycarbonyl group or a phenolic hydroxy group. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the modification of the hydroxy structure in the component (A) is etherification or esterification. [8] The photosensitive resin composition according to any one of [1] to [7], wherein in the component (A), when the total number of modified hydroxy structures and the number of unmodified hydroxy structures is T1 and the number of modified hydroxy structures is S1, the modification rate u1 (%) defined by the following formula (1) is 10 to 90%:

number

[10] In formula (A-1), A 1 is a tetravalent organic group represented by the following formula (X-3): [ka] (In formula (X-3), nc represents an integer of 0 or more. 1 , ring Ar 2 and ring Ar 3 each independently represents an aromatic carbocyclic ring having 6 to 10 carbon atoms. 1 and L 2 each independently represents a single bond, an oxygen atom, an ester bond, or an alkylene group having 1 to 5 carbon atoms which may have a halogen atom as a substituent; L 1 and nc pieces of L 2 At least one of the groups is an oxygen atom or an ester bond. * represents a bond.

[11] The photosensitive resin composition according to any one of [1] to

[10] , wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-2): [ka] (In formula (A-2), M represents an integer of 1 or more. q1 and q2 each independently represent an integer of 1 to 4. A 1 Each X independently represents a tetravalent organic group having an ether structure or an ester structure. Each X independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 4 to 20 carbon atoms, or a divalent group consisting of a combination thereof. Y 1 and Y 2 each independently represents a hydroxy group, a hydroxycarbonyl group, a group represented by the following formula (X-1), or a group represented by the following formula (X-2), and Y in the M repeating units 1 and Y 2 At least one of the above is a group represented by the following formula (X-1) or a group represented by the following formula (X-2). [ka] (In formula (X-1), R 14 , R 15 and R 16L each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. a1 represents an oxygen atom or an ester bond. p1 represents an integer of 0 to 10. * represents a bond. [ka] In formula (X-2), ring Z represents an aliphatic hydrocarbon ring having 3 to 20 carbon atoms which may have a substituent. 24 , R 25 and R 26 L each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. a2 represents an oxygen atom or an ester bond. p2 represents an integer of 0 to 10. * represents a bond.

[12] The photosensitive resin composition according to

[11] , wherein in formula (A-2), X is an alkylene group having 1 to 5 carbon atoms.

[13] In formula (A-2), Y 1 and Y 2 are each independently a hydroxy group, a hydroxycarbonyl group, or a group represented by the above formula (X-1), In formula (X-1), R 14 is a hydrogen atom or a methyl group, and R 15 is a hydrogen atom, and R 16 is a hydrogen atom, and p1 is 1.

[14] The photosensitive resin composition according to any one of [1] to

[13] , wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-2-1): [ka] (In formula (A-2-1), M represents an integer of 1 or more. R a1 and R a2 each independently represents a hydrogen atom or a group represented by the following formula (X-4), and R a1 and R a2 At least one of the above is a group represented by the following formula (X-4): [ka]

[15] The photosensitive resin composition according to any one of [1] to

[13] , wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-2-2): [ka] (In formula (A-2-2), M represents an integer of 1 or more. R a1 and R a2 each independently represents a hydrogen atom or a group represented by the following formula (X-4), and R a1 and R a2 At least one of the above is a group represented by the following formula (X-4): [ka]

[16] The photosensitive resin composition according to any one of [1] to

[13] , wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-2-3): [ka] (In formula (A-2-3), M represents an integer of 1 or more. R a1 and R a2 each independently represents a hydrogen atom or a group represented by the following formula (X-4), and R a1 and R a2 At least one of the above is a group represented by the following formula (X-4): [ka]

[17] The photosensitive resin composition according to any one of [1] to

[13] , wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-2-4): [ka] (In formula (A-2-4), M represents an integer of 1 or more. R a1 and R a2 each independently represents a hydrogen atom or a group represented by the following formula (X-4), and Ra1 and R a2 At least one of the above is a group represented by the following formula (X-4): [ka]

[18] The photosensitive resin composition according to any one of [1] to

[17] , wherein at least one terminal of the main chain of the component (A) is a maleimide group.

[19] The photosensitive resin composition according to any one of [1] to

[18] , wherein both ends of the main chain of the component (A) are maleimide groups.

[20] The photosensitive resin composition according to any one of [1] to

[19] , wherein the component (A) is a polyimide polymer represented by the following formula (A-4): [ka] (In formula (A-4), M represents an integer of 1 or more. A 1 A each independently represents a tetravalent organic group having an ether structure or an ester structure. 2 each independently represents a divalent organic group having one or more groups selected from a hydroxy group, a hydroxycarbonyl group, an oxycarbonyl group having an ethylenically unsaturated bond, and an alkoxy group having an ethylenically unsaturated bond, and A in the M+1 repeating units 2 At least one of the groups has one or more groups selected from an oxycarbonyl group having an ethylenically unsaturated bond and an alkoxy group having an ethylenically unsaturated bond.

[21] The photosensitive resin composition according to any one of [9] to

[20] , wherein m defined in the following formula (2) is 90 to 100, where M is the number of repetitions of the structural unit represented by formula (A-1) and, if other structural units are present, N is the number of repetitions of the other structural units:

number

[22] The photosensitive resin composition according to any one of [9] to

[21] , wherein in formula (A-1), M is an integer of 5 to 200.

[23] The photosensitive resin composition according to any one of [1] to

[22] , further comprising (B) a photopolymerization initiator.

[24] The photosensitive resin composition according to any one of [1] to

[23] , further comprising (C) a crosslinking agent.

[25] The photosensitive resin composition according to any one of [1] to

[24] , further comprising (D) an adhesion aid.

[26] The photosensitive resin composition according to any one of [1] to

[25] , further comprising (E) a sensitizer.

[27] The photosensitive resin composition according to any one of [1] to

[26] , further comprising (F) a surfactant.

[28] A photosensitive film comprising a support and a photosensitive resin composition layer formed on the support, the photosensitive resin composition layer comprising the photosensitive resin composition according to any one of [1] to

[27] .

[29] A semiconductor package substrate comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of [1] to

[27] .

[30] A semiconductor device comprising the semiconductor package substrate according to

[29] .

[31] A step of forming a photosensitive resin composition layer containing the photosensitive resin composition according to any one of [1] to

[27] on a circuit board; and a step of irradiating the photosensitive resin composition layer with actinic rays to perform development; A method for manufacturing a semiconductor package substrate, comprising: [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a photosensitive resin composition that can be developed in an alkaline aqueous solution at room temperature in a short time and that can give a cured product that exhibits an excellent linear thermal expansion coefficient, glass transition temperature, and elongation at break at a low curing temperature, as well as a photosensitive film, semiconductor package substrate, semiconductor device, and method for producing a semiconductor package substrate, all of which are obtained using the photosensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0013] The photosensitive resin composition of the present invention, and the photosensitive film, semiconductor package substrate, semiconductor device, and method for manufacturing a semiconductor package substrate obtained using the photosensitive resin composition will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and can be modified and implemented as desired within the scope of the claims and their equivalents.

[0014] In the following description, unless otherwise specified, the expressions "XX to YY" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way.

[0015] In the following description, "dielectric constant" refers to "relative dielectric constant" unless otherwise specified.

[0016] In the following description, unless otherwise specified, the term "optionally substituted" in reference to a compound or group means both a case where the hydrogen atoms of the compound or group are not substituted with a substituent and a case where some or all of the hydrogen atoms of the compound or group are substituted with a substituent. Furthermore, when the number of constituent atoms or carbon atoms of the compound or group is stated, the number of constituent atoms or carbon atoms does not include the number of constituent atoms or carbon atoms of substituents, unless otherwise specified.

[0017] In the following description, the content of each component in the photosensitive resin composition represents a value when the non-volatile components in the photosensitive resin composition are taken as 100 mass %, unless otherwise specified.

[0018] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) a polyimide polymer having a structure derived from a tetracarboxylic dianhydride having an ether structure or an ester structure and a structure derived from a diamine having a hydroxy structure, in which some or all of the hydroxy structures have been modified with a structure derived from an epoxy compound having an ethylenically unsaturated bond (hereinafter also referred to as a "polyimide polymer having a specific structure"). By incorporating component (A) into the photosensitive resin composition, it is possible to develop the composition with an alkaline aqueous solution at room temperature in a short time, and to obtain a cured product that exhibits an excellent linear thermal expansion coefficient, glass transition temperature, and elongation at break at a low curing temperature.

[0019] The photosensitive resin composition is suitable as a negative photosensitive resin composition. In a negative photosensitive resin composition, a crosslinking reaction or the like occurs in the area irradiated with actinic rays, and the composition becomes insoluble in a developer. Therefore, it becomes possible to selectively remove the photosensitive resin composition from areas other than those where the crosslinking reaction has progressed during development, and a negative pattern can be advantageously formed. The remaining area after development has sufficient strength due to the crosslinking reaction or the like, and can be used as is as an insulating layer or the like in the form of a permanent film.

[0020] The photosensitive resin composition may further contain optional components in combination with component (A). Examples of optional components include (B) a photopolymerization initiator, (C) a crosslinking agent, (D) an adhesion aid, (E) a sensitizer, (F) a surfactant, (G) a solvent, and (H) other additives. Each component contained in the photosensitive resin composition will be described in detail below.

[0021] <(A) Polyimide polymer having a specific structure> The photosensitive resin composition contains, as component (A), a polyimide polymer having a structure derived from a tetracarboxylic dianhydride having an ether structure or an ester structure and a structure derived from a diamine having a hydroxy structure, in which some or all of the hydroxy structures have been modified with a structure derived from an epoxy compound having an ethylenically unsaturated bond. Component (A) may be used alone or in combination of two or more.

[0022] When the component (A) has a structure derived from a tetracarboxylic dianhydride with an asymmetric structure represented by the following formula (P-1) and a structure derived from a diamine with an asymmetric structure represented by the following formula (Q-1), the structural units of the polyimide polymer may be four types of positional isomers represented by the following formulas (PQ-1) to (PQ-4). [ka]

[0023] In the following description, polyimide polymers may be described using structural formulas. Unless otherwise specified, the expression of any one of formulas (PQ-1) to (PQ-4) is considered to encompass all structures of formulas (PQ-1) to (PQ-4). That is, a "polyimide polymer having a structural unit represented by formula (PQ-1)" means a "polyimide polymer having one or more structural units selected from formulas (PQ-1) to (PQ-4)." In the case of a polyimide polymer having two or more structural units selected from formulas (PQ-1) to (PQ-4), this term also includes polyimide polymers in which the two or more structural units are copolymerized in any of the following ways: random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, and ordered copolymerization.

[0024] Because component (A) is a polyimide polymer, an imidization reaction after insulating layer formation is unnecessary, allowing the photosensitive resin composition to be cured at low temperatures. Because component (A) has a structure derived from a tetracarboxylic dianhydride having an ether or ester structure, the linear expansion coefficient of the cured product of the photosensitive resin composition can be reduced and the glass transition temperature can be increased. This is presumably because the ether or ester structure of component (A) improves the molecular orientation of component (A), making it less susceptible to free movement even when heated. Because component (A) has a structure derived from a diamine having a hydroxyl structure, the solubility of the photosensitive resin composition in alkaline aqueous solutions is improved, allowing it to be developed with alkaline aqueous solutions. By modifying some or all of the hydroxyl structures in component (A) with a structure derived from an epoxy compound having an ethylenically unsaturated bond, the ethylenically unsaturated bonds in component (A) react and polymerize upon exposure, effectively reducing the solubility of the cured product of the photosensitive resin composition in a developer. In other words, the resolution of the photosensitive resin composition can be maintained.

[0025] Component (A) has a structure derived from a tetracarboxylic dianhydride having an ether structure or an ester structure. The tetracarboxylic dianhydride-derived structure in component (A) may have both an ether structure and an ester structure. The tetracarboxylic dianhydride-derived structure in component (A) preferably has an ether structure from the viewpoint of further reducing the linear expansion coefficient of the cured product and further increasing the glass transition temperature of the cured product, and preferably has an ester structure from the viewpoint of further increasing the elongation at break of the cured product and further decreasing the dielectric constant of the cured product.

[0026] Examples of tetracarboxylic acid dianhydrides having an ether structure or an ester structure include aliphatic tetracarboxylic acid dianhydrides having an ether structure or an ester structure and aromatic tetracarboxylic acid dianhydrides having an ether structure or an ester structure, with aromatic tetracarboxylic acid dianhydrides having an ether structure or an ester structure being preferred. Furthermore, as the tetracarboxylic acid dianhydride having an ether structure or an ester structure, tetracarboxylic acid dianhydrides having an ether structure are preferred from the viewpoint of further reducing the linear expansion coefficient of the cured product and further increasing the glass transition temperature of the cured product, and tetracarboxylic acid dianhydrides having an ester structure are preferred from the viewpoint of further increasing the elongation at break of the cured product and further decreasing the dielectric constant of the cured product. Furthermore, the number of carbon atoms in the tetracarboxylic acid dianhydride having an ether structure or an ester structure is preferably 10 to 54, more preferably 10 to 30, and even more preferably 15 to 25.

[0027] Examples of aromatic tetracarboxylic dianhydrides having an ether structure or an ester structure include 4,4'-oxydiphthalic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA), 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate (TAHQ), and the like, with 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA) or 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate (TAHQ) being preferred. One type of tetracarboxylic dianhydride having an ether structure or an ester structure may be used alone, or two or more types may be used in combination.

[0028] Component (A) has a structure derived from a diamine having a hydroxy structure. Examples of the hydroxy structure include an alcoholic hydroxy group, a phenolic hydroxy group, a hydroxycarbonyl group, and a sulfonic acid group, with a phenolic hydroxy group or a hydroxycarbonyl group being preferred. From the viewpoint of further increasing the glass transition temperature of the cured product and further shortening the development time of the photosensitive resin composition layer with an alkaline aqueous solution, a hydroxycarbonyl group is more preferred. From the viewpoint of further reducing the linear expansion coefficient of the cured product, further improving the elongation at break of the cured product, and further reducing the dielectric constant and dielectric dissipation factor of the cured product, a phenolic hydroxy group is more preferred. The diamine having a hydroxy structure preferably has 6 to 50 carbon atoms, more preferably 6 to 30, even more preferably 10 to 20, and particularly preferably 12 to 18. Examples of diamines having a hydroxy structure include diamines (1) to (10) represented by the following formulas, with diamine (1) or diamine (4) being preferred. [ka]

[0029] Some or all of the hydroxy structures in component (A) are modified with a structure derived from an epoxy compound having an ethylenically unsaturated bond. Here, "modified" refers to the reaction of the hydroxy structures in component (A) with the epoxy groups of the epoxy compound having an ethylenically unsaturated bond to form a bond. The modification of the hydroxy structures is preferably etherification or esterification. Typically, when the hydroxy structure is an alcoholic hydroxy group or a phenolic hydroxy group, the modification is etherification, and when the hydroxy structure is a hydroxycarbonyl group or a sulfonic acid group, the modification is esterification. The ester used in the esterification is preferably a carboxylic acid ester or a sulfonic acid ester, and more preferably a carboxylic acid ester.

[0030] The epoxy compound having an ethylenically unsaturated bond is preferably glycidyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate, more preferably glycidyl (meth)acrylate, and even more preferably glycidyl methacrylate. "(Meth)acrylate" encompasses methacrylate and acrylate.

[0031] In component (A), when the total number of modified hydroxy structures and the number of unmodified hydroxy structures is T1 and the number of modified hydroxy structures is S1, the modification rate u1 (%) defined by the following formula (1) is preferably 1 to 100%. The lower limit of the modification rate u1 is more preferably 5% or more or 10% or more, even more preferably 15% or more or 20% or more, and particularly preferably 25% or more or 30% or more. The upper limit of the modification rate u1 is more preferably 90% or less or 80% or less, even more preferably 70% or less or 60% or less, and particularly preferably 50% or less or 45% or less.

number

[0032] The component (A) is preferably a polyimide polymer having a structural unit represented by the following formula (A-1). [ka] (In formula (A-1), M represents an integer of 1 or more. A 1 A each independently represents a tetravalent organic group having an ether structure or an ester structure. 2 each independently represents a divalent organic group having one or more groups selected from a hydroxy group, a hydroxycarbonyl group, an oxycarbonyl group having an ethylenically unsaturated bond, and an alkoxy group having an ethylenically unsaturated bond, and A in the M repeating units 2 At least one of the groups has one or more groups selected from an oxycarbonyl group having an ethylenically unsaturated bond and an alkoxy group having an ethylenically unsaturated bond.

[0033] In formula (A-1), M represents an integer of 1 or more. The upper limit of M is preferably 150 or less, more preferably 100 or less, even more preferably 80 or less or 60 or less, and particularly preferably 50 or less or 40 or less. The lower limit of M is preferably 2 or more, 3 or more, or 4 or more, more preferably 5 or more, even more preferably 6 or more or 7 or more, and particularly preferably 10 or more.

[0034] In formula (A-1), A 1 A each independently represents a tetravalent organic group having an ether structure or an ester structure. 1 is preferably a tetravalent organic group having an ether structure from the viewpoint of further reducing the linear expansion coefficient of the cured product and further increasing the glass transition temperature of the cured product, and is preferably a tetravalent organic group having an ester structure from the viewpoint of further increasing the elongation at break of the cured product and further decreasing the dielectric constant of the cured product.

[0035] A 1 The number of carbon atoms in A is preferably 6 to 50. 1 The lower limit of the number of carbon atoms in A is more preferably 8 or more, 10 or more, or 12 or more, even more preferably 14 or more, or 16 or more, and particularly preferably 18 or more. 1 The upper limit of the number of carbon atoms is preferably 40 or less, more preferably 36 or less, even more preferably 32 or less, and particularly preferably 28 or less.

[0036] A 1 is preferably a tetravalent organic group having constituent atoms selected from carbon, oxygen, hydrogen, nitrogen, sulfur, and fluorine atoms, more preferably a tetravalent organic group having constituent atoms selected from carbon, oxygen, and hydrogen atoms, and even more preferably a tetravalent organic group having constituent atoms selected from carbon, oxygen, and hydrogen atoms.

[0037] A 1is preferably a tetravalent organic group having an aromatic ring. The term "aromatic ring" refers to a ring conforming to Hückel's rule, in which the number of electrons contained in the π-electron system on the ring is 4r+2 (r is a natural number), and includes monocyclic aromatic rings and fused aromatic rings in which two or more monocyclic aromatic rings are fused. The aromatic ring is preferably a monocyclic aromatic ring. The aromatic ring may be an aromatic carbocycle having only carbon atoms as ring-constituting atoms, or an aromatic heterocycle having heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms as ring-constituting atoms in addition to carbon atoms. The aromatic ring is preferably an aromatic carbocycle. The number of carbon atoms in the aromatic ring is preferably 3 or more, more preferably 4 or more or 5 or more, and even more preferably 6 or more. The upper limit of the number of carbon atoms in the aromatic ring is preferably 24 or less, more preferably 18 or less or 14 or less, and even more preferably 10 or less. The number of carbon atoms does not include the number of carbon atoms of substituents.

[0038] Examples of the monocyclic aromatic ring include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a furazan ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, an imidazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a pyridazine ring. Examples of fused aromatic rings in which two or more monocyclic aromatic rings are fused include a naphthalene ring, an anthracene ring, a phenanthrene ring, a benzofuran ring, an isobenzofuran ring, an indole ring, an isoindole ring, a benzothiophene ring, a benzimidazole ring, an indazole ring, a benzoxazole ring, a benzisoxazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, an acridine ring, a quinazoline ring, a cinnoline ring, a phthalazine ring, a pyridothiazole ring, a benzotriazole ring, an imidazopyridine ring, a triazopyridine ring, a purine ring, etc. As the aromatic ring, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred.

[0039] A 1 is preferably a tetravalent organic group represented by the following formula (X-3). [ka] (In formula (X-3), nc represents an integer of 0 or more. 1 , ring Ar 2 and ring Ar 3 each independently represents an aromatic carbocyclic ring having 6 to 10 carbon atoms. 1 and L 2 each independently represents a single bond, an oxygen atom, an ester bond, or an alkylene group having 1 to 5 carbon atoms which may have a halogen atom as a substituent; L 1 and nc pieces of L 2 At least one of the groups is an oxygen atom or an ester bond. * represents a bond.

[0040] In formula (X-3), nc represents an integer of 0 or more. nc is preferably 1 or more, and more preferably 2 or more. The upper limit of nc is not particularly limited, but may be, for example, 50 or less, 40 or less, 30 or less, 20 or less, 10 or less, 5 or less, or 3 or less.

[0041] In formula (X-3), ring Ar 1 , ring Ar 2 and ring Ar 3 each independently represents an aromatic carbocyclic ring having 6 to 10 carbon atoms. Preferred embodiments of the aromatic ring are as described above, and a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. When nc is an integer of 2 or more, two or more rings Ar 2 exists, but the two or more rings Ar 2 may be the same or different from each other.

[0042] In formula (X-3), L 1 and L 2 each independently represents a single bond, an oxygen atom, an ester bond, or an alkylene group having 1 to 5 carbon atoms which may have a halogen atom as a substituent. When nc is an integer of 2 or more, two or more L 2 There are two or more L 2 may be the same or different from each other.

[0043] The number of carbon atoms in the alkylene group which may have a halogen atom as a substituent is 1 to 5, and preferably 1 to 3. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a 2,2-propylidene group (dimethylmethylene group), among which a methylene group or a 2,2-propylidene group is preferred, and a 2,2-propylidene group is more preferred.

[0044] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom, a chlorine atom, or a bromine atom is preferred, a fluorine atom or a chlorine atom is more preferred, and a fluorine atom is even more preferred.

[0045] Examples of the alkylene group having a halogen atom as a substituent include a difluoromethylene group, a tetrafluoroethylene group, a 1,2-difluoroethylene group, and a hexafluoro-2,2-propylidene group.

[0046] Among these, L 1 and L 2 is preferably an oxygen atom, an ester bond, or an alkylene group having 1 to 5 carbon atoms, and more preferably an oxygen atom, an ester bond, or a 2,2-propylidene group.

[0047] In formula (X-3), L 1 and nc pieces of L 2 At least one of is an oxygen atom or an ester bond.

[0048] In formula (A-1), A 2 each independently represents a divalent organic group having one or more groups selected from a hydroxy group, a hydroxycarbonyl group, an oxycarbonyl group having an ethylenically unsaturated bond, and an alkoxy group having an ethylenically unsaturated bond. The oxycarbonyl group having an ethylenically unsaturated bond represents a monovalent group represented by the following formula (X-5), and the alkoxy group having an ethylenically unsaturated bond represents a monovalent group represented by the following formula (X-6). [ka] (In formula (X-5) and formula (X-6), R a5 and R a6 represents a monovalent group having an ethylenically unsaturated bond. * represents a bond.

[0049] A 2 The number of carbon atoms of A is preferably 6 to 50. The lower limit of the number of carbon atoms of A is more preferably 8 or more, 10 or more, or 12 or more, and even more preferably 14 or more. 1 The upper limit of the number of carbon atoms is more preferably 45 or less or 40 or less, further preferably 36 or less, and particularly preferably 32 or less or 30 or less.

[0050] A 2 is preferably a divalent organic group having constituent atoms selected from carbon, oxygen, hydrogen, nitrogen, sulfur, and fluorine atoms, more preferably a divalent organic group having constituent atoms selected from carbon, oxygen, and hydrogen atoms, and even more preferably a divalent organic group having constituent atoms selected from carbon, oxygen, and hydrogen atoms.

[0051] A 2 is preferably a divalent organic group having an aromatic ring. Preferred embodiments of the aromatic ring are as described above, and a benzene ring or a naphthalene ring is preferred, with a benzene ring being more preferred.

[0052] In formula (A-1), A in M ​​repeating units 2 At least one of the groups has one or more groups selected from an oxycarbonyl group having an ethylenically unsaturated bond and an alkoxy group having an ethylenically unsaturated bond.

[0053] The component (A) is preferably a polyimide polymer having a structural unit represented by the following formula (A-2). [ka] (In formula (A-2), M represents an integer of 1 or more. q1 and q2 each independently represent an integer of 1 to 4. A 1Each X independently represents a tetravalent organic group having an ether structure or an ester structure. Each X independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 4 to 20 carbon atoms, or a divalent group consisting of a combination thereof. Y 1 and Y 2 each independently represents a hydroxy group, a hydroxycarbonyl group, a group represented by the following formula (X-1), or a group represented by the following formula (X-2), and Y in the M repeating units 1 and Y 2 At least one of the above is a group represented by the following formula (X-1) or a group represented by the following formula (X-2). [ka] (In formula (X-1), R 14 , R 15 and R 16 L each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. a1 represents an oxygen atom or an ester bond. p1 represents an integer of 0 to 10. * represents a bond. [ka] In formula (X-2), ring Z represents an aliphatic hydrocarbon ring having 3 to 20 carbon atoms which may have a substituent. 24 , R 25 and R 26 L each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. a2 represents an oxygen atom or an ester bond. p2 represents an integer of 0 to 10. * represents a bond.

[0054] In formula (A-2), M represents an integer of 1 or more and is the same as M in formula (A-1).

[0055] In formula (A-2), q1 and q2 each independently represent an integer of 1 to 4. q1 and q2 are preferably integers of 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0056] In formula (A-2), A 1 each independently represents a tetravalent organic group having an ether structure or an ester structure, and A in formula (A-1) 1 is the same as

[0057] In formula (A-2), X's each independently represent a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 4 to 20 carbon atoms, or a divalent group consisting of a combination thereof. The bonding position of X may be any of the ortho-position, meta-position, and para-position based on the bonding position of the nitrogen atom of the polyimide, but from the viewpoint of significantly achieving the effects of the present invention, the meta-position or para-position is preferred.

[0058] The number of carbon atoms in the alkylene group which may have a halogen atom as a substituent is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. Examples of the alkylene group include a methylene group, an ethylene group, an ethylidene group, a 1,2-propylene group, a 1,3-propylene group, a 1,1-propylidene group, and a 2,2-propylidene group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom, a chlorine atom, or a bromine atom is preferred, a fluorine atom or a chlorine atom is more preferred, and a fluorine atom is even more preferred.

[0059] Examples of the alkylene group having a halogen atom as a substituent include a difluoromethylene group, a tetrafluoroethylene group, a 1,2-difluoroethylene group, and a hexafluoro-2,2-propylidene group.

[0060] The number of carbon atoms in the arylene group is preferably 6 to 15, more preferably 6 to 10, and even more preferably 6. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, and a biphenylene group (-C6H4-C6H4-).

[0061] Examples of divalent groups formed from these combinations include divalent groups formed from a combination of an ester bond and an alkylene group having 1 to 20 carbon atoms, and divalent groups formed from a combination of an ester bond and an arylene group having 4 to 20 carbon atoms. Examples of such groups include a carbonyloxymethylene group, a carbonyloxyethylene group, a carbonyloxypropylene group, a carbonyloxyphenylene group, a carbonyloxynaphthylene group, and a carbonyloxybiphenylene group.

[0062] Among these, X is preferably an alkylene group having 1 to 5 carbon atoms which may have a halogen atom as a substituent, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group or a 2,2-propylidene group.

[0063] In formula (A-2), Y 1 and Y 2 each independently represents a hydroxy group, a hydroxycarbonyl group, a group represented by the above formula (X-1), or a group represented by the above formula (X-2). 1 and Y 2 may be the same or different. 1 and Y 2 are each preferably independently a hydroxy group, a hydroxycarbonyl group, or a group represented by the above formula (X-1). 1 and Y 2 The bonding position of may be any of the ortho, meta, and para positions based on the bonding position of the nitrogen atom of the polyimide, but the ortho position is preferred from the viewpoint of achieving the remarkable effects of the present invention.

[0064] R in formula (X-1) 14 , R 15 and R 16 R each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. 14 , R15 and R 16 is preferably a hydrogen atom or a methyl group. 14 is preferably a hydrogen atom or a methyl group, more preferably a methyl group. 15 R is more preferably a hydrogen atom. 16 is more preferably a hydrogen atom.

[0065] L in formula (X-1) a1 represents an oxygen atom or an ester bond.

[0066] In formula (X-1), p1 represents an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 1.

[0067] Examples of the group represented by formula (X-1) include a group represented by formula (X-1-1) and a group represented by formula (X-1-2), etc. In the formula, * represents a bond. [ka]

[0068] Ring Z in formula (X-2) represents an aliphatic hydrocarbon ring having 3 to 20 carbon atoms, which may have a substituent. The aliphatic hydrocarbon ring may be monocyclic or polycyclic. The aliphatic hydrocarbon ring may be a saturated aliphatic hydrocarbon ring such as a cycloalkane ring, or an unsaturated aliphatic hydrocarbon ring such as a cycloalkene ring. The number of carbon atoms in the aliphatic hydrocarbon ring is preferably 3 to 10. Examples of the aliphatic hydrocarbon ring include monocycloalkane rings such as a cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, and cyclooctane ring; bicycloalkane rings such as a decalin ring and a norbornane ring; spiroalkane rings such as a spirononane ring; monocycloalkene rings such as a cyclobutene ring, cyclopropene ring, cyclohexene ring, cyclohexadiene ring, cycloheptene ring, and cyclooctene ring; bicycloalkene rings such as a norbornene ring and a norbornadiene ring; and spiroalkene rings such as a spirononene ring. Of these, a cycloalkane ring is preferred, a monocycloalkane ring is more preferred, and a cyclohexane ring is even more preferred.

[0069] Examples of substituents that the aliphatic hydrocarbon ring in ring Z may have include linear, branched, or cyclic C1-C10 alkyl groups such as methyl, ethyl, n-propyl, 2-propyl, n-butyl, s-butyl, i-butyl, t-butyl, cyclopentyl, and cyclohexyl; halogen atoms such as fluorine, chlorine, and bromine; alkoxy groups having C1-C10 such as methoxy, ethoxy, propoxy, t-butoxy, and phenoxy; hydroxy; and halogen-substituted alkyl groups such as trifluoromethyl, with alkyl groups being preferred. The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). The substituents may be contained alone or in combination of two or more.

[0070] R in formula (X-2) 24 , R 25 and R 26R each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. 24 , R 25 and R 26 is preferably a hydrogen atom or a methyl group. 24 is preferably a hydrogen atom or a methyl group, more preferably a methyl group. 25 R is more preferably a hydrogen atom. 26 is more preferably a hydrogen atom.

[0071] L in formula (X-2) a2 represents an oxygen atom or an ester bond.

[0072] In formula (X-2), p2 represents an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 1.

[0073] Examples of the group represented by formula (X-2) include a group represented by formula (X-2-1), a group represented by formula (X-2-2), a group represented by formula (X-2-3), and a group represented by formula (X-2-4), etc. In the formula, * represents a bond. [ka]

[0074] In formula (A-2), Y in M ​​repeating units 1 and Y 2 At least one of the above is a group represented by the formula (X-1) or a group represented by the formula (X-2).

[0075] Specific examples of the component (A) having a structural unit represented by formula (A-2) include a polyimide polymer having a structural unit represented by formula (A-2-1) below, a polyimide polymer having a structural unit represented by formula (A-2-2) below, a polyimide polymer having a structural unit represented by formula (A-2-3) below, and a polyimide polymer having a structural unit represented by formula (A-2-4) below. a1 and R a2 is a group represented by the following formula (X-4)" means that in the M repeating units, there are M R a1 and M R a2 are present, and at least one of the total 2M is a group represented by the following formula (X-4). [ka] (In formula (A-2-1), M represents an integer of 1 or more. R a1 and R a2 each independently represents a hydrogen atom or a group represented by the following formula (X-4), and R a1 and R a2 At least one of the above is a group represented by the following formula (X-4): [ka] [ka] (In formula (A-2-2), M represents an integer of 1 or more. R a1 and R a2 each independently represents a hydrogen atom or a group represented by the above formula (X-4), and R a1 and R a2 At least one of the above is a group represented by the above formula (X-4). [ka] (In formula (A-2-3), M represents an integer of 1 or more. R a1 and R a2each independently represents a hydrogen atom or a group represented by the above formula (X-4), and R a1 and R a2 At least one of the above is a group represented by the above formula (X-4). [ka] (In formula (A-2-4), M represents an integer of 1 or more. R a1 and R a2 each independently represents a hydrogen atom or a group represented by the above formula (X-4), and R a1 and R a2 At least one of the above is a group represented by the above formula (X-4).

[0076] Preferably, at least one of the terminals of the main chain of component (A) is a maleimide group, and more preferably, both are maleimide groups. By providing maleimide groups at the terminals, the dielectric constant and dielectric dissipation factor of the cured product can be reduced. This is presumably because providing maleimide groups at the terminals reduces the polarity of component (A).

[0077] The component (A) is preferably a polyimide polymer represented by the following formula (A-3) or a polyimide polymer represented by the following formula (A-4). [ka] (In formula (A-3) and formula (A-4), M represents an integer of 1 or more. 1 A each independently represents a tetravalent organic group having an ether structure or an ester structure. 2 each independently represents a divalent organic group having one or more groups selected from a hydroxy group, a hydroxycarbonyl group, an oxycarbonyl group having an ethylenically unsaturated bond, and an alkoxy group having an ethylenically unsaturated bond, and A in the M+1 repeating units 2 At least one of the groups has one or more groups selected from an oxycarbonyl group having an ethylenically unsaturated bond and an alkoxy group having an ethylenically unsaturated bond.

[0078] In formula (A-3) and formula (A-4), M represents an integer of 1 or more and is the same as M in formula (A-1).

[0079] In formula (A-3) and formula (A-4), A 1 each independently represents a tetravalent organic group having an ether structure or an ester structure, and A in formula (A-1) 1 is the same as

[0080] In formula (A-3) and formula (A-4), A 2 each independently represents a divalent organic group having one or more groups selected from a hydroxy group, a hydroxycarbonyl group, an oxycarbonyl group having an ethylenically unsaturated bond, and an alkoxy group having an ethylenically unsaturated bond, and A in formula (A-1) 2 In addition, in formula (A-3) and formula (A-4), A in M+1 repeating units is the same as 2 At least one of the groups has one or more groups selected from an oxycarbonyl group having an ethylenically unsaturated bond and an alkoxy group having an ethylenically unsaturated bond.

[0081] The component (A) is preferably a polyimide polymer represented by the following formula (A-5) or a polyimide polymer represented by the following formula (A-6). [ka] (In formula (A-5) and formula (A-6), M represents an integer of 1 or more. q1 and q2 each independently represent an integer of 1 to 4. A 1 Each X independently represents a tetravalent organic group having an ether structure or an ester structure. Each X independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 4 to 20 carbon atoms, or a divalent group consisting of a combination thereof. Y 1 and Y 2each independently represents a hydroxy group, a hydroxycarbonyl group, a group represented by the above formula (X-1), or a group represented by the above formula (X-2), and Y in the M+1 repeating units 1 and Y 2 At least one of the above is a group represented by the formula (X-1) or a group represented by the formula (X-2).

[0082] In formula (A-5) and formula (A-6), M represents an integer of 1 or more and is the same as M in formula (A-1).

[0083] In formula (A-5) and formula (A-6), q1 and q2 each independently represent an integer of 1 to 4 and are the same as q1 and q2 in formula (A-2).

[0084] In formula (A-5) and formula (A-6), A 1 each independently represents a tetravalent organic group having an ether structure or an ester structure, and A in formula (A-1) 1 is the same as

[0085] In formula (A-5) and formula (A-6), X each independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 4 to 20 carbon atoms, or a divalent group consisting of a combination thereof, and is the same as X in formula (A-2).

[0086] In formula (A-5) and formula (A-6), Y 1 and Y 2 each independently represents a hydroxy group, a hydroxycarbonyl group, a group represented by the above formula (X-1), or a group represented by the above formula (X-2), and Y 1 and Y 2 In addition, in formula (A-5) and formula (A-6), Y in M+1 repeating units is the same as 1 and Y 2 At least one of the above is a group represented by the formula (X-1) or a group represented by the formula (X-2).

[0087] Specific examples of the polyimide polymer represented by formula (A-6) include a polyimide polymer represented by the following formula (A-6-1), a polyimide polymer represented by the following formula (A-6-2), a polyimide polymer represented by the following formula (A-6-3), and a polyimide polymer represented by the following formula (A-6-4). [ka] (In formula (A-6-1), M represents an integer of 1 or more. R a1 and R a2 each independently represents a hydrogen atom or a group represented by the following formula (X-4), and R a1 and R a2 At least one of the above is a group represented by the following formula (X-4): [ka] [ka] (In formula (A-6-2), M represents an integer of 1 or more. R a1 and R a2 each independently represents a hydrogen atom or a group represented by the above formula (X-4), and R a1 and R a2 At least one of the above is a group represented by the above formula (X-4). [ka] (In formula (A-6-3), M represents an integer of 1 or more. R a1 and R a2 each independently represents a hydrogen atom or a group represented by the above formula (X-4), and R a1 and R a2 At least one of the above is a group represented by the above formula (X-4). [ka] (In formula (A-6-4), M represents an integer of 1 or more. R a1 and R a2each independently represents a hydrogen atom or a group represented by the above formula (X-4), and R a1 and R a2 At least one of the above is a group represented by the above formula (X-4).

[0088] Component (A) may have a polyamic acid and / or polyamic acid ester structure in addition to a polyimide structure, as long as the effects of the present invention are not impaired. The polyamic acid and / or polyamic acid ester structure may be present when the imidization reaction does not proceed completely in step (ii) of the <Production Method of Component (A)> described below.

[0089] Furthermore, when component (A) is a polyimide polymer having a structural unit represented by the above formula (A-1), it may have other structures in addition to the structural unit represented by the above formula (A-1), as long as the effects of the present invention are not impaired. Examples of other structures include a structure derived from a tetracarboxylic dianhydride having neither an ether structure nor an ester structure, and a structure derived from a diamine having no hydroxy structure. When the structural unit represented by the above formula (A-1) is copolymerized with another structure, the copolymerization may be in any form. Examples of the copolymerization form include random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, and ordered copolymerization.

[0090] In component (A), when the repeating number of the structural unit represented by formula (A-1) is M and the repeating number of the other structural unit, if any, is N, m defined in the following formula (2) is preferably 90 to 100. Examples of the other structural unit include the aforementioned polyamic acid and / or polyamic acid ester structure. M is more preferably 95 or more or 96 or more, even more preferably 97 or more, and particularly preferably 98 or more.

number

[0091] From the viewpoint of significantly achieving the effects of the present invention, the weight average molecular weight of component (A) is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 14,000 or more or 16,000 or more, and particularly preferably 20,000 or more. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less, even more preferably 200,000 or less or 100,000 or less, and particularly preferably 50,000 or less or 30,000 or less. The weight average molecular weight can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0092] From the viewpoint of obtaining excellent limiting resolution and obtaining a cured product with excellent physical properties, the content of component (A) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass. There is no particular upper limit, but it may be 100% by mass, or it may be 99% by mass or less, 95% by mass or less, or 90% by mass or less, etc.

[0093] <Method of manufacturing component (A)> There are no particular limitations on the method for producing component (A). Component (A) can be obtained, for example, by reacting a tetracarboxylic dianhydride having an ether structure or an ester structure, a diamine having a hydroxy structure, and an epoxy compound having an ethylenically unsaturated bond.

[0094] As the tetracarboxylic dianhydride having an ether structure or an ester structure, the above-mentioned 4,4'-oxydiphthalic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA), 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate (TAHQ), etc. can be used. As the diamine having a hydroxy structure, the above-mentioned diamines (1) to (10), etc. can be used. As the epoxy compound having an ethylenically unsaturated bond, the above-mentioned glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, etc. can be used.

[0095] Specifically, for example, component (A) is (1-1) a step of charging a diamine having a hydroxy structure, a tetracarboxylic dianhydride having an ether structure or an ester structure, and an organic solvent into a reaction vessel and heating the mixture; (2-1) a step of heating at a temperature higher than that of step (1-1); (3) adding a polymerization inhibitor and an epoxy compound having an ethylenically unsaturated bond to a reaction vessel and heating the mixture; The composition can be produced by a production method including the steps of:

[0096] In step (1-1), a diamine having a hydroxy structure, a tetracarboxylic dianhydride having an ether structure or an ester structure, and an organic solvent are charged into a reaction vessel and heated to produce a polyamic acid. For example, a separable flask can be used as the reaction vessel, and an oil bath or the like can be used for heating. The organic solvent is preferably an ester-based organic solvent, more preferably a lactone-based organic solvent, and particularly preferably γ-butyrolactone. The heating temperature is preferably 50 to 60°C, and the reaction time is preferably 15 to 20 hours. In step (1-1), when the ratio of the number of moles of diamine charged to the number of moles of tetracarboxylic dianhydride charged (diamine / tetracarboxylic dianhydride) is greater than 1, a polyimide polymer represented by the above formula (A-3) having amine terminals can be produced. The lower limit of the ratio of the number of moles of diamine charged to the number of moles of tetracarboxylic dianhydride charged (diamine / tetracarboxylic dianhydride) is preferably 1 or more or more than 1, more preferably 1.01 or more or 1.02 or more, even more preferably 1.03 or more or 1.04 or more, and particularly preferably 1.05 or more. The upper limit is preferably 1.3 or less, more preferably 1.2 or less or 1.19 or less, and even more preferably 1.18 or less or 1.17 or less.

[0097] When producing the component (A) in which at least one of the ends of the main chain is a maleimide group, the following step may be carried out between the steps (1-1) and (2): (1-2) adding maleic anhydride and reacting; may be performed.

[0098] The heating temperature in step (1-2) is preferably 50 to 60° C., and the reaction time is preferably 2 to 10 hours.

[0099] In step (2-1), heating is performed at a temperature higher than in step (1-1), and a polyimide polymer is produced by an imidization reaction of the polyamic acid produced in step (1-1). The reaction temperature in step (2-1) is preferably 120 to 200°C, and the heating time is preferably 3 to 10 hours. In step (2-1), it is preferable to carry out the reaction while removing the produced water. Methods for removing the produced water include a method using a Dean-Stark trap and a method of adding a solvent that forms an azeotrope with water. Examples of solvents that form an azeotrope with water include toluene and benzene, with toluene being preferred.

[0100] The reaction in step (2-1) may be carried out without a catalyst, but it is preferable to add a catalyst, and more preferably a base catalyst or an acid catalyst. Adding a catalyst can increase the yield of the imidization reaction, resulting in a cured product with superior dielectric properties. The amount of catalyst added is preferably 0.1 to 5% by mass, where the total amount of the diamine and tetracarboxylic dianhydride is taken as 100% by mass.

[0101] Examples of base catalysts include pyridine, triethylamine, tributylamine, N,N-dimethylaminopyridine (DMAP), N-methylimidazole (MIMZ), etc. Examples of acid catalysts include acetic acid, oxalic acid, benzoic acid, 3,5-dihydroxybenzoic acid, etc., with benzoic acid being preferred.

[0102] Between step (2-1) and step (3), (2-2) isolating the polyimide polymer; (2-3) dissolving the isolated polyimide polymer in an organic solvent; may be implemented.

[0103] In step (2-2), the polyimide polymer is isolated. The polyimide polymer can be isolated, for example, by pouring the solution obtained in step (2-1) into pure water to precipitate the polyimide polymer, and filtering the resulting solid. The solid obtained by filtration is preferably dried under reduced pressure to volatilize the solvent.

[0104] In the step (2-3), the polyimide polymer obtained in the step (2-2) is dissolved in an organic solvent, preferably so that the polyimide polymer concentration is 20 to 30 mass %.

[0105] In step (3), a polymerization inhibitor and an epoxy compound having an ethylenically unsaturated bond are added to a reaction vessel and heated to modify part or all of the structure derived from the diamine having a hydroxy structure. In step (3), it is preferable to add the polymerization inhibitor and then add the epoxy compound having an ethylenically unsaturated bond.

[0106] The polymerization inhibitor is preferably diluted and dissolved in an organic solvent before addition. Examples of the polymerization inhibitor include 4-tert-butylpyrocatechol, tert-butylhydroquinone, 1,4-benzoquinone, dibutylhydroxytoluene, 1,1-diphenyl-2-picrylhydrazyl free radical, hydroquinone, mequinol, phenothiazine, and 4-methoxyphenol, with 4-methoxyphenol being preferred. The amount of the polymerization inhibitor added is preferably 0.01 to 5% by mass, more preferably 0.05 to 0.5% by mass, based on 100% by mass of the total amount of the diamine and tetracarboxylic dianhydride, in order to prevent gelation of the polymer components during the reaction.

[0107] The amount of the epoxy compound having an ethylenically unsaturated bond added is preferably 0.3 to 10 equivalents, more preferably 0.5 to 3 equivalents, relative to the hydroxy structure derived from the diamine. The epoxy compound having an ethylenically unsaturated bond is preferably added using a dropping funnel or the like.

[0108] In step (3), it is preferable to add an epoxy compound having an ethylenically unsaturated bond, followed by adding a base catalyst and heating. The heating temperature is preferably 70 to 100°C, and the heating time is preferably 12 to 20 hours. Examples of base catalysts include 2-ethyl-4-methylimidazole (2E4MZ), 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), N,N-dimethylaminopyridine (DMAP), N-methylimidazole (MIMZ), triethylamine, tributylamine, pyridine, quaternary onium salts such as tetrabutylammonium bromide (Bu4NBr), and crown ethers such as 18-crown-6 ether, with 2-ethyl-4-methylimidazole (2E4MZ) being preferred. From the viewpoint of efficiently progressing the modification reaction, the amount of the base catalyst added is preferably 0.01 to 5 mass%, more preferably 0.05 to 3 mass%, and even more preferably 0.1 to 2 mass%, when the total amount of the diamine compound and the tetracarboxylic dianhydride is taken as 100 mass%.

[0109] <(B) Photopolymerization initiator> The photosensitive resin composition may contain a (B) photopolymerization initiator as an optional component, and preferably contains a (B) photopolymerization initiator. When the photosensitive resin composition is irradiated with actinic rays, the ethylenically unsaturated bonds in the (A) component polymerize, and the portions where crosslinking reactions or the like have occurred are insoluble in the developer, even when the photosensitive resin composition contains only the (A) component. This makes it possible to selectively remove the photosensitive resin composition from portions other than those where crosslinking reactions have progressed during development, thereby forming a negative pattern. Here, the (B) component generates radicals upon irradiation with actinic rays. The presence of radicals in the photosensitive resin composition allows the crosslinking reactions or the like to proceed more efficiently, thereby more effectively forming a negative pattern. The (B) component may be used alone or in combination of two or more. The (B) component is a different component from the (A) and (C) components.

[0110] (B) Photopolymerization initiators include intramolecular cleavage-type photopolymerization initiators and hydrogen abstraction-type photopolymerization initiators, with intramolecular cleavage-type photopolymerization initiators being preferred. Intramolecular cleavage-type photopolymerization initiators are photopolymerization initiators that generate radicals by intramolecular cleavage, while hydrogen abstraction-type photopolymerization initiators are photopolymerization initiators that generate radicals by exchanging hydrogen or electrons between two molecules.

[0111] Examples of the intramolecular cleavage photopolymerization initiator include an α-aminoketone-based photopolymerization initiator, a phosphine oxide-based photopolymerization initiator, an α-hydroxyketone-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, a benzyl-based photopolymerization initiator, a benzyl ketal-based photopolymerization initiator, a benzoin-based photopolymerization initiator, a peroxide-based photopolymerization initiator, a titanocene-based photopolymerization initiator, and a cyanide-based photopolymerization initiator. From the viewpoint of photosensitivity, an oxime ester-based photopolymerization initiator or a phosphine oxide-based photopolymerization initiator is preferred, and an oxime ester-based photopolymerization initiator is more preferred.

[0112] Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and aromatic biimidazole-based photopolymerization initiators.

[0113] Examples of the α-aminoketone photopolymerization initiator include 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-methyl-1-(4-hexylphenyl)-2-morpholinopropan-1-one, 2-ethyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, and N-arylglycines such as N-phenylglycine.

[0114] The phosphine oxide photopolymerization initiator is preferably an acylphosphine photopolymerization initiator. Examples of the acylphosphine photopolymerization agent include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, and polyoxyethylene glycerin ether tris[phenyl(2,4,6-trimethylbenzoyl)phosphinate] (Polymeric TPO-L), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is preferred.

[0115] Examples of the α-hydroxyketone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropanone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one.

[0116] Examples of the oxime ester photopolymerization initiator include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (OXE01), [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate (OXE02), 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-benzoyl)oxime, and 1,3-diphenyl Examples of the ethoxybenzyloxyimino compound include 1-phenyl-3-ethoxypropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, and α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide. Of these, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (OXE01) or [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate (OXE02) is preferred, and [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate (OXE02) is more preferred.

[0117] Examples of the benzyl-based photopolymerization initiator include benzyl.

[0118] Examples of the benzyl ketal photopolymerization initiator include benzyl dimethyl ketal (2,2-dimethoxy-2-phenylacetophenone) and benzyl-β-methoxyethyl acetal.

[0119] Examples of the benzoin-based photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0120] Examples of peroxide-based photopolymerization initiators include benzoyl perchloride.

[0121] Examples of the titanocene photopolymerization initiator include bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanocene. Examples of the cyanide-based photopolymerization initiator include α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide.

[0122] Examples of the benzophenone-based photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and fluorenone.

[0123] Examples of the acetophenone-based photopolymerization initiator include 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone.

[0124] Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone.

[0125] Examples of aromatic biimidazole photopolymerization initiators include 2,2'-bis-(2-chlorophenyl)4,5,4',5'-tetraphenyl-1,2'-biimidazole.

[0126] Component (B) can be a commercially available product, such as "Irgacure-OXE01," "Irgacure-OXE02," "Irgacure-OXE04," and "IrgacureTPO" manufactured by BASF, "Omnirad907," "Omnirad369," "Omnirad379," "Omnirad379EG," "Omnirad819," and "OmniradTPO" manufactured by IGM, and "N-1919" manufactured by ADEKA.

[0127] From the viewpoints of improving photosensitivity, improving patterning ability, and further improving the physical properties of the photosensitive resin composition layer after curing the photosensitive resin composition, the lower limit of the mass ratio of component (B) to component (A) [component (B) / component (A)] is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and particularly preferably 0.015 or more. The upper limit is preferably 0.2 or less, more preferably 0.1 or less, even more preferably 0.05 or less, and particularly preferably 0.03 or less or 0.025 or less.

[0128] When the photosensitive resin composition contains the component (B), from the viewpoints of improving photosensitivity, improving patterning ability, and improving the physical properties of the photosensitive resin composition layer after curing the photosensitive resin composition, the lower limit of the mass ratio of the component (A) to the component (B) [component (A) / component (B)] is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more. The upper limit is preferably 60 or less, more preferably 50 or less, and even more preferably 45 or less.

[0129] When the photosensitive resin composition contains component (B), the content of component (B) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 1.5% by mass or more, based on 100% by mass of the nonvolatile components of the photosensitive resin composition, from the viewpoints of improving photosensitivity, improving patterning ability, and improving the physical properties of the photosensitive resin composition layer after curing the photosensitive resin composition. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less or 2% by mass or less.

[0130] From the viewpoint of achieving a significant effect of the present invention, the total content of the components (A) and (B) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more or 85% by mass or more, when the total non-volatile components of the photosensitive resin composition is taken as 100% by mass. There is no particular upper limit, but it may be 100% by mass or may be 99% by mass or less, 97% by mass or less, 95% by mass or less, or 93% by mass or less.

[0131] <(C) Crosslinking Agent> The photosensitive resin composition may contain a crosslinking agent (C) as an optional component, and preferably contains a crosslinking agent (C). As described above, when the photosensitive resin composition is irradiated with actinic rays, even when only the component (A) is contained, the ethylenically unsaturated bonds in the component (A) polymerize, and the portions where crosslinking reactions have occurred are insoluble in the developer. This makes it possible to selectively remove the photosensitive resin composition from portions other than those where the crosslinking reaction has progressed during development, thereby forming a negative pattern. Here, if the photosensitive resin composition also contains the component (C), the crosslinking reaction of the component (C) also progresses upon irradiation with actinic rays, allowing the crosslinking reaction to proceed more efficiently, resulting in the formation of a negative pattern more advantageously. The component (C) may be used alone or in combination of two or more. Furthermore, the component (C) does not include components that correspond to the component (A).

[0132] As component (C), a compound capable of promoting a crosslinking reaction can be used. The lower limit of the number of reactive sites per molecule of component (C) that undergo a crosslinking reaction (hereinafter sometimes referred to as the "number of functional groups") is preferably 1 or more, more preferably 2 or more. The upper limit of the number of functional groups is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 6 or less, 4 or less, or 3 or less. Examples of component (C) include (C1) a compound having an ethylenically unsaturated bond, (C2) a compound having two or more epoxy groups, a nitrogen-containing compound containing two or more methylol groups and / or alkoxymethyl groups, a condensate of a nitrogen-containing compound containing two or more methylol groups and / or alkoxymethyl groups, and a phenol compound having two or more methylol groups or alkoxymethyl groups. Examples of nitrogen-containing compounds containing two or more methylol groups and / or alkoxymethyl groups include melamine compounds containing two or more methylol groups and / or alkoxymethyl groups, guanamine compounds containing two or more methylol groups and / or alkoxymethyl groups, glycoluril compounds containing two or more methylol groups and / or alkoxymethyl groups, etc. As component (C), (C1) a compound having an ethylenically unsaturated bond or (C2) a compound having two or more epoxy groups is preferred, and (C1) a compound having an ethylenically unsaturated bond is more preferred.

[0133] <(C1) Compound having an ethylenically unsaturated bond> In one embodiment of the present invention, component (C) preferably includes (C1) a compound having an ethylenically unsaturated bond. When component (C) is a compound having (C1) an ethylenically unsaturated bond, it is more preferable that at least one of the carbon atoms at the α-position of the ethylenically unsaturated bond is a carbon atom of a carbonyl group or a carbon atom of an aromatic group. The carbon atom at the α-position of the ethylenically unsaturated bond refers to the first carbon atom adjacent to the carbon atom bonded by a carbon-carbon double bond.

[0134] The ethylenically unsaturated bond represents a carbon-carbon double bond. Therefore, component (C1) may contain a group having an ethylenically unsaturated bond (hereinafter, referred to as "ethylenically unsaturated group" as appropriate). The ethylenically unsaturated group is typically a monovalent group, such as a vinyl group, allyl group, propargyl group, butenyl group, styryl group, ethynyl group, phenylethynyl group, maleimide group, nadimide group, or (meth)acryloyl group. From the viewpoint of photoradical polymerization reactivity, a (meth)acryloyl group or an allyl group is preferred. The term "(meth)acryloyl group" encompasses methacryloyl groups, acryloyl groups, and combinations thereof. Since component (C1) contains an ethylenically unsaturated group, it is photoradical polymerizable. For photoradical polymerization under general conditions, compounds having a carbonyl group or an aromatic group at at least one α-position of the ethylenically unsaturated bond are preferred. The lower limit for the number of ethylenically unsaturated groups per molecule of component (C1) is preferably at least 1, and more preferably at least 2. The upper limit is preferably at most 30, more preferably at most 20, even more preferably at most 10, and particularly preferably at most 6, 4, or 3. Furthermore, when component (C1) contains two or more ethylenically unsaturated groups per molecule, these ethylenically unsaturated groups may be the same or different.

[0135] In one embodiment of the present invention, the component (C1) is preferably a compound represented by the following formula (C-1). [ka] (In formula (C-1), R 1c each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; Z 1c each independently represents a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, an arylene group which may contain an oxygen atom, or a linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom; A 1c represents an organic group with a valence of nc, where nc is a positive integer of 2 to 6.

[0136] R1c are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1-butyl group, a s-butyl group, and a t-butyl group. Among these, R 1c is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

[0137] Z 1c each independently represents a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, an arylene group which may contain an oxygen atom, or a linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom.

[0138] As the linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkylene group having 1 to 10 carbon atoms is preferred, and a linear or branched alkylene group having 1 to 6 carbon atoms is more preferred. Examples of such alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, with a methylene group being preferred. The alkylene group may also be an oxyalkylene group containing an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 20. [ka]

[0139] The arylene group which may contain an oxygen atom is preferably an arylene group having 6 to 24 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, still more preferably an arylene group having 6 to 12 carbon atoms, and particularly preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include a phenylene group and a naphthylene group. The arylene group may also contain an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 4. [ka]

[0140] As the linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom, a linear or branched alkenylene group having 2 to 10 carbon atoms is preferred, and a linear or branched alkenylene group having 2 to 6 carbon atoms is more preferred. Examples of such alkenylene groups include ethenylene, propenylene, butenylene, pentenylene, and hexenylene, with propenylene being preferred. The alkenylene group may also be an oxyalkenylene group containing an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 10. [ka]

[0141] Among them, Z 1c As the alkyl group, a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom is preferred, a methylene group or an oxyalkylene group is more preferred, and a methylene group is even more preferred.

[0142] A 1c represents an organic group with a valence of nc. 1cExamples of A include linear, cyclic, or branched C1-10 nc-valent hydrocarbon groups which may contain an oxygen atom, nc-valent groups derived from bisphenol, nc-valent groups derived from fluorene, nc-valent groups derived from tricyclodecane, and nc-valent groups derived from an isocyanuric group. Examples of nc-valent hydrocarbon groups which may contain an oxygen atom include nc-valent aliphatic hydrocarbon groups which may contain an oxygen atom, and nc-valent aromatic hydrocarbon groups which may contain an oxygen atom. nc-valent aliphatic hydrocarbon groups which may contain an oxygen atom are preferred, and when nc is 2, for example, an alkylene group is preferred. A 1c Specific examples of the group represented by include the following: In the formula, "*" represents a bond. [ka]

[0143] nc represents a positive integer of 2 to 6. nc is preferably a positive integer of 2 to 5, more preferably a positive integer of 2 to 4, and even more preferably 2 or 3.

[0144] In one embodiment of the present invention, the component (C1) is preferably a compound represented by the following formula (C-2). [ka] (In formula (C-2), R 2c each independently represents a hydrogen atom or a methyl group.

[0145] In formula (C-2), R 2c represents a hydrogen atom or a methyl group, and a methyl group is preferred.

[0146] Specific examples of the component (C1) represented by formula (C-1) include the following compounds (CL-1) to (CL-13). As the component (C1), the compound (CL-1), the compound (CL-2), the compound (CL-12) or the compound (CL-13) is preferred, the compound (CL-1) or the compound (CL-2) is more preferred, and the compound (CL-2) is even more preferred. [ka] [ka] [ka]

[0147] Component (C1) can be a commercially available product. Examples of commercially available products of component (C1) represented by formula (C-1) above include NK Ester D-TMP, TMPT, A-TMPT, 4G, 9G, 14G, 23G, and DCP manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd., and SR209, CN2301, and CN2304 manufactured by Sartomer Japan.

[0148] In one embodiment of the present invention, the component (C1) is preferably a compound represented by the following formula (C-3). [ka] (In formula (C-3), R 11c , R 12c , R 13c , R 14c , R 15c and R 16c each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms; Z c represents a divalent organic group.

[0149] R 11c , R 12c , R 13c , R 14c , R 15c and R 16cR each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. Examples of the hydrocarbon group having 1 to 3 carbon atoms include an aliphatic hydrocarbon group having 1 to 3 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include a saturated aliphatic hydrocarbon group, such as an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, with a methyl group being preferred. 11c , R 12c , R 13c , R 14c , R 15c and R 16c is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0150] Z c represents a divalent organic group. Examples of divalent organic groups include divalent aliphatic hydrocarbon groups, divalent aromatic hydrocarbon groups, divalent groups containing heteroatoms, and divalent groups consisting of a combination of two or more of these. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms.

[0151] The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic. The divalent aliphatic hydrocarbon group may be saturated or unsaturated. The divalent aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Examples of the divalent aliphatic hydrocarbon group include alkylene groups, alkenylene groups, and alkynylene groups. Examples of the alkylene group include methylene groups, ethylene groups, propylene groups, butylene groups, pentylene groups, and hexylene groups. Examples of the alkenylene group include ethenylene groups, propenylene groups, butenylene groups, pentenylene groups, and hexenylene groups. Examples of the alkynylene group include ethynylene groups and propynylene groups.

[0152] The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. Examples of the divalent aromatic hydrocarbon group include an arylene group, and examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a naphthylene group, an anthracenylene group, a biphenylene group, and a 9,9-diphenyl-9H-fluorenylene group.

[0153] Examples of the divalent group containing a hetero atom include -O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -C(=O)-NH-, -S(=O)2-, -S(=O)2-O-, and the groups shown below. [ka] (* represents a bond.)

[0154] Examples of the divalent group consisting of two or more combinations include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent group containing a heteroatom bonded together; a divalent aromatic hydrocarbon group and a divalent group containing a heteroatom bonded together; and a divalent aliphatic hydrocarbon group and a divalent group containing a heteroatom bonded together. Specific examples of the divalent group consisting of two or more combinations include the following groups (X-7) to (X-13). In the groups (X-7) to (X-13), * represents a bond. As the divalent group consisting of two or more combinations, groups (X-7) to (X-10) are preferred, groups (X-7) and (X-8) are more preferred, and groups (X-7) are even more preferred. [ka]

[0155] Z cThe divalent organic group in the formula (I) may have a substituent. Examples of the substituent include linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl; halogen atoms such as fluorine, chlorine, and bromine; alkoxy groups having 1 to 10 carbon atoms, such as methoxy, ethoxy, and propoxy; hydroxy groups; and halogen-substituted alkyl groups, such as trifluoromethyl. The above-mentioned substituents may further have a secondary substituent. The substituent may be contained alone or in combination of two or more. When the divalent organic group has a substituent, the substituent is preferably a hydroxy group.

[0156] Specific examples of the component (C1) represented by formula (C-3) include triallyl isocyanurate, triallyl cyanurate, 1,3,5-triallylhexahydro-1,3,5-triazine, diallylpropyl isocyanurate, diallyl 1,4-cyclohexanedicarboxylate, 9,9-bis(4-allyloxyphenyl)fluorene, 2,2-bis(allyloxymethyl)-1-butanol, and compounds represented by the following formulas (C-3-1) to (C-3-4). Of these, the compound represented by formula (C-3-1) or the compound represented by formula (C-3-2) is preferred, and the compound represented by formula (C-3-1) is more preferred. [ka]

[0157] The component (C1) represented by formula (C-3) can be a commercially available product, such as "BANI-X" and "BANI-M" manufactured by Maruzen Petrochemical Co., Ltd., "DAD" manufactured by Nisshoku Techno Fine Chemical Co., Ltd., or "DPNG" manufactured by Kuraray Co., Ltd.

[0158] When the photosensitive resin composition contains component (C), and component (C) contains a compound (C1) having an ethylenically unsaturated bond, from the viewpoint of significantly achieving the effects of the present invention and obtaining excellent limiting resolution, the mass ratio of component (C1) to component (A) [component (C1) / component (A)] is preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.05 or more, and particularly preferably 0.07 or more. The upper limit is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.2 or less, and particularly preferably 0.15 or less or 0.1 or less.

[0159] When the photosensitive resin composition contains the component (C), and the component (C) contains the compound (C1) having an ethylenically unsaturated bond, from the viewpoint of significantly achieving the effects of the present invention and obtaining excellent limiting resolution, the lower limit of the mass ratio of the component (A) to the component (C1) [component (A) / component (C1)] is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, and particularly preferably 10 or more. The upper limit is preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less.

[0160] When the photosensitive resin composition contains the component (B) and the component (C), and the component (C) contains a compound (C1) having an ethylenically unsaturated bond, from the viewpoint of significantly achieving the effects of the present invention and obtaining excellent limiting resolution, the lower limit of the mass ratio of the component (C1) to the component (B) [component (C1) / component (B)] is preferably at least 1, more preferably at least 2, even more preferably at least 3, and particularly preferably at least 3.5. The upper limit is preferably at most 20, more preferably at most 10, even more preferably at most 8, and particularly preferably at most 6.

[0161] When the photosensitive resin composition contains component (C), and component (C) contains a compound (C1) having an ethylenically unsaturated bond, the content of component (C1) is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more, based on 100% by mass of the non-volatile components of the photosensitive resin composition, from the viewpoint of significantly achieving the effects of the present invention and obtaining excellent limiting resolution. The upper limit is preferably 40% by mass or less, 30% by mass or less, or 20% by mass or less, more preferably 15% by mass or less, even more preferably 12% by mass or less, or 10% by mass or less.

[0162] <(C2) Compounds having two or more epoxy groups> In one embodiment of the present invention, the component (C) may contain (C2) a compound having two or more epoxy groups. By including (C2) a compound having two or more epoxy groups in the photosensitive resin composition, the strength of the cured product of the photosensitive resin composition can be improved. The component (C2) may be used alone or in combination of two or more.

[0163] The number of epoxy groups contained in one molecule of component (C2) is 2 or more, and preferably 10 or less, more preferably 8 or less, and even more preferably 4 or less, from the viewpoints of obtaining excellent limiting resolution and improving the mechanical strength of the cured product of the photosensitive resin composition.

[0164] Examples of the component (C2) include aromatic epoxy compounds such as bixylenol-type epoxy compounds, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol S-type epoxy compounds, bisphenol AF-type epoxy compounds, trisphenol-type epoxy compounds, naphthol novolac-type epoxy compounds, phenol novolac-type epoxy compounds, tert-butyl-catechol-type epoxy compounds, naphthalene-type epoxy compounds, naphthol-type epoxy compounds, anthracene-type epoxy compounds, cresol novolac-type epoxy compounds, biphenyl-type epoxy compounds, and naphthylene ether-type epoxy compounds; aliphatic epoxy compounds such as epoxy compounds having a butadiene structure, cyclohexane-type epoxy compounds, cyclohexanedimethanol-type epoxy compounds, trimethylol-type epoxy compounds, and tetraphenylethane-type epoxy compounds; alicyclic epoxy compounds; heterocyclic epoxy compounds; glycidyl ether-type epoxy compounds; and glycidylamine-type epoxy compounds. Among these, from the viewpoint of significantly obtaining the effects of the present invention, aromatic epoxy compounds are preferred, and among aromatic epoxy compounds, naphthalene-type epoxy compounds or bisphenol A-type epoxy compounds are preferred, with naphthalene-type epoxy compounds being more preferred.

[0165] Specific examples of aromatic epoxy compounds include "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy compounds) manufactured by DIC Corporation; "828US," "jER828EL," "825," and "Epikote 828EL" (bisphenol A-type epoxy compounds) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F-type epoxy compounds) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy compound) manufactured by Mitsubishi Chemical Corporation; and "ZX105" manufactured by Nippon Steel Chemical & Material Co., Ltd. 9 (a mixture of bisphenol A and bisphenol F epoxy compounds); DIC's "HP4032H" (a naphthalene-type epoxy compound); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy compounds); DIC's "N-690" (a cresol novolac-type epoxy compound); DIC's "N-695" (a cresol novolac-type epoxy compound); Nippon Kayaku's "EPPN-502H" (a trisphenol-type epoxy compound); Nippon Kayaku's "NC7000L" " (naphthol novolac type epoxy compound); "NC3000H", "NC3000", "NC3000L", and "NC3100" (biphenyl type epoxy compounds) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthol type epoxy compound) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol novolac type epoxy compound) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL6121" (biphenyl type epoxy compound) manufactured by Mitsubishi Chemical Corporation; "YX4000H", "YX4000", and "YX4000HK" manufactured by Mitsubishi Chemical Corporation (bixylenol-type epoxy compound); "YX8800" manufactured by Mitsubishi Chemical Corporation (anthracene-type epoxy compound); "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals Co., Ltd.; "YL7760" manufactured by Mitsubishi Chemical Corporation (bisphenol AF-type epoxy compound); "YL7800" manufactured by Mitsubishi Chemical Corporation (fluorene-type epoxy compound); "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A-type epoxy compound); and "jER1031S" manufactured by Mitsubishi Chemical Corporation (tetraphenylethane-type epoxy compound).

[0166] The epoxy equivalent of the (C2) compound having two or more epoxy groups is preferably 50 g / eq to 5000 g / eq, more preferably 50 g / eq to 3000 g / eq, even more preferably 80 g / eq to 2000 g / eq, and even more preferably 110 g / eq to 1000 g / eq. Within this range, the crosslink density of the cured product of the photosensitive resin composition is sufficient, resulting in an insulating layer with low surface roughness. The epoxy equivalent is the mass of a resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0167] From the viewpoint of significantly achieving the desired effects of the present invention, the weight average molecular weight (Mw) of the component (C2) is preferably from 100 to 5000, more preferably from 250 to 3000, and even more preferably from 400 to 1500. The weight average molecular weight can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0168] When the photosensitive resin composition contains component (C), and component (C) contains a compound having two or more epoxy groups (C2), the content of component (C2) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, based on 100% by mass of the nonvolatile components of the photosensitive resin composition, from the viewpoint of obtaining excellent limiting resolution and improving the mechanical strength of the cured product. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0169] When the photosensitive resin composition contains component (C), from the viewpoint of significantly achieving the effects of the present invention and obtaining excellent limiting resolution, the mass ratio of component (C) to component (A) [component (C) / component (A)] is preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.05 or more, and particularly preferably 0.07 or more. The upper limit is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.2 or less, and particularly preferably 0.15 or less or 0.1 or less.

[0170] When the photosensitive resin composition contains the component (C), from the viewpoint of significantly achieving the effects of the present invention and obtaining excellent limiting resolution, the lower limit of the mass ratio of the component (A) to the component (C) [component (A) / component (C)] is preferably at least 1, more preferably at least 3, even more preferably at least 5, and particularly preferably at least 10. The upper limit is preferably at most 25, more preferably at most 20, and even more preferably at most 15.

[0171] When the photosensitive resin composition contains the component (B) and the component (C), from the viewpoint of significantly achieving the effects of the present invention and obtaining excellent limiting resolution, the lower limit of the mass ratio of the component (C) to the component (B) [component (C) / component (B)] is preferably at least 1, more preferably at least 2, even more preferably at least 3, and particularly preferably at least 3.5. The upper limit is preferably at most 20, more preferably at most 10, even more preferably at most 8, and particularly preferably at most 6.

[0172] When the photosensitive resin composition contains component (C), the content of component (C) is, from the viewpoint of significantly achieving the effects of the present invention and obtaining excellent limiting resolution, preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or more, based on 100% by mass of the non-volatile components of the photosensitive resin composition. The upper limit is preferably 40% by mass or less, 30% by mass or less, or 20% by mass or less, more preferably 15% by mass or less, even more preferably 12% by mass or less, or 10% by mass or less.

[0173] From the viewpoint of achieving a significant effect of the present invention, the total content of components (A) and (C) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more or 80% by mass or more, and particularly preferably 85% by mass or more, 90% by mass or more, or 95% by mass or more, when the total non-volatile components of the photosensitive resin composition is taken as 100% by mass. There is no particular upper limit, but it may be 100% by mass or may be 99% by mass or less, 98% by mass or less, 97% by mass or less, etc.

[0174] To achieve the effects of the present invention more significantly, the total content of components (A), (B), and (C) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more or 80% by mass or more, and particularly preferably 85% by mass or more, 90% by mass or more, 95% by mass or more, or 97% by mass or more, based on 100% by mass of the non-volatile components of the photosensitive resin composition. There is no particular upper limit, but it may be 100% by mass, or may be 99.9% by mass or less, 99.5% by mass or less, or 99% by mass or less, for example.

[0175] <(D) Adhesion aid> The photosensitive resin composition may contain an adhesion aid (D) as an optional component, and preferably contains an adhesion aid (D). By adding the adhesion aid (D) to the photosensitive resin composition, the adhesion strength between the substrate and the cured product of the photosensitive resin composition can be improved. The component (D) may be used alone or in combination of two or more. Furthermore, the component (D) is a component different from the components (A) to (C).

[0176] The (D) adhesion aid can be a compound that improves the adhesion strength between the substrate and the film formed using the photosensitive resin composition. Examples of the (D) adhesion aid include a silane coupling agent, an aluminum-based adhesion aid, and a triazole-based adhesion aid, with a silane coupling agent being preferred.

[0177] Examples of the silane coupling agent include amino-based silane coupling agents, imide-based silane coupling agents, amide-based silane coupling agents, epoxy-based silane coupling agents, mercapto-based silane coupling agents, vinyl-based silane coupling agents, (meth)acrylic silane coupling agents, styryl-based silane coupling agents, isocyanurate-based silane coupling agents, ureido-based silane coupling agents, isocyanate-based silane coupling agents, triazine-based silane coupling agents, and acid anhydride-based silane coupling agents, and epoxy-based silane coupling agents are preferred.

[0178] Examples of amino-based silane coupling agents include γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, and N-phenylaminopropyltrimethoxysilane.

[0179] Examples of epoxy-based silane coupling agents include γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and diethoxy-3-glycidoxypropylmethylsilane, with γ-glycidoxypropyltrimethoxysilane being preferred.

[0180] Examples of the mercapto-based silane coupling agent include γ-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethylmethyldimethoxysilane, 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopropylethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethylsilane, mercaptopropyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltrippropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2-mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltrippropoxysilane, and the like.

[0181] Examples of the (meth)acrylic silane coupling agent include 3-methacryloxypropyldimethoxymethylsilane and 3-methacryloxypropyltrimethoxysilane.

[0182] Examples of imide-based silane coupling agents include N-(3-diethoxymethylsilylpropyl) succinimide.

[0183] Examples of amide-based silane coupling agents include N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, and benzene-1,4-bis(N-3-triethoxysilyl]propylamide)-2,5-dicarboxylic acid.

[0184] Examples of acid anhydride-based silane coupling agents include 3-(triethoxysilyl)propyl succinic anhydride, 3-(trialkoxysilyl)propyl succinic anhydride, and the like.

[0185] Examples of the ureido-based silane coupling agent include 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-(3-triethoxysilylpropyl)urea, and N-(3-trimethoxysilylpropyl)urea.

[0186] Examples of triazine-based silane coupling agents include compounds having an aminotriazine ring and an ethoxysilyl group.

[0187] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0188] Examples of triazole-based adhesion aids include 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-amino-5-mercapto-1H-1,2,4-triazole, 5-amino-1,2,4-triazole-3-carboxylic acid, and 3,5-diphenyl-1,2,4-triazole.

[0189] (D) The adhesion aid can be a commercially available product. Examples of commercially available products include "KBM-403" (3-glycidoxypropyltrimethoxysilane), "KBM-803" (3-mercaptopropyltrimethoxysilane), "LS1375" (3-mercaptopropylmethyldimethoxysilane), and "LS3610" (N-(3-triethoxysilylpropyl)urea) manufactured by Shin-Etsu Chemical Co., Ltd.; "Sila-Ace S810" (3-mercaptopropyltrimethoxysilane) manufactured by Chisso Corporation; and "SIM6475.0" (3-mercaptopropyltriethoxysilane) manufactured by Azmax Corporation. ethoxysilane), "SIM6474.0" (3-mercaptopropylmethyldimethoxysilane), "SIM6473.5C" (mercaptomethyltrimethoxysilane), "SIM6473.0" (mercaptomethylmethyldimethoxysilane), "SIU9055.0" (N-(3-triethoxysilylpropyl)urea), "SIU9058.0" (N-(3-trimethoxysilylpropyl)urea); "VD-5" (a compound having an aminotriazine ring and an ethoxysilyl group) manufactured by Shikoku Chemicals Corporation, and the like.

[0190] When the photosensitive resin composition contains component (D), the content of component (D) is, from the viewpoints of substrate adhesion and mechanical strength, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.15% by mass or more, based on 100% by mass of the non-volatile components of the photosensitive resin composition. The upper limit is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less or 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

[0191] When the photosensitive resin composition contains component (D), from the viewpoints of substrate adhesion and mechanical strength, the mass ratio of component (D) to component (A) [component (D) / component (A)] is preferably 0.0001 or more, more preferably 0.0005 or more, even more preferably 0.001 or more, and particularly preferably 0.0015 or more. The upper limit is preferably 0.1 or less, more preferably 0.05 or less, even more preferably 0.01 or less, and particularly preferably 0.005 or less.

[0192] When the photosensitive resin composition contains the component (B) and the component (D), from the viewpoints of substrate adhesion and mechanical strength, the mass ratio of the component (D) to the component (B) [component (D) / component (B)] is preferably 0.005 or more, more preferably 0.01 or more, even more preferably 0.05 or more, and particularly preferably 0.08 or more. The upper limit is preferably 2 or less or 1 or less, more preferably 0.5 or less, even more preferably 0.3 or less, and particularly preferably 0.2 or less.

[0193] When the photosensitive resin composition contains the components (C) and (D), from the viewpoints of substrate adhesion and mechanical strength, the mass ratio of the component (D) to the component (C) [component (D) / component (C)] is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and particularly preferably 0.02 or more. The upper limit is preferably 1 or less or 0.5 or less, more preferably 0.1 or less, even more preferably 0.05 or less, and particularly preferably 0.03 or less.

[0194] <(E) Sensitizer> The photosensitive resin composition may contain a sensitizer (E) as an optional component, and preferably contains a sensitizer (E). The inclusion of a sensitizer (E) makes it possible to further improve the photosensitivity of the photosensitive resin composition. The component (E) may be used alone or in combination of two or more. Furthermore, the component (E) does not include components that fall under the category of component (B), and is a component that is different from components (A), (C), and (D).

[0195] The component (E) may be a compound capable of improving the photosensitivity of the photosensitive resin composition. Examples of such compounds include anthracenes such as anthracene-9,10-dibutyl ether, 9,10-diacetyloxyanthracene, and 9,10-bis(n-octanoyloxy)anthracene; benzophenones such as Michler's ketone, 4,4'-bis(diethylamino)benzophenone, and 4-morpholinobenzophenone; 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylamino)benzophenone; Cyclic alkanes such as 2,6-bis(4'-diethylaminobenzal)cyclohexanone and 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone; chalcones such as 4,4'-bis(dimethylamino)chalcone and 4,4'-bis(diethylamino)chalcone; indanones such as p-dimethylaminocinnamylideneindanone and p-dimethylaminobenzylideneindanone; 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-di Thiazoles such as 2-(p-dimethylaminophenylvinylene)benzothiazole and 2-(p-dimethylaminophenylvinylene)isonaphthothiazole; acetones such as 1,3-bis(4'-dimethylaminobenzal)acetone and 1,3-bis(4'-diethylaminobenzal)acetone; coumarins such as 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, and 3-ethoxycarbonyl-7-diethylaminocoumarin; amines such as N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, and isoamyl diethylaminobenzoate;Heterocycles such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 1-phenyl-5-mercaptotetrazole, and 1-p-hydroxyphenyl-5-mercaptotetrazole; and styrenes such as 2-(p-dimethylaminobenzoyl)styrene.

[0196] Examples of anthracenes include anthracene ether compounds, substituted acyloxyanthracene compounds, and alkoxycarbonyloxyanthracene compounds.

[0197] Examples of anthracene ether compounds include anthracene monoether compounds and anthracene diether compounds, with anthracene diether compounds being preferred. In the case of anthracene monoether compounds, the substitution position of the ether may be any one of the 1st, 2nd, and 9th positions of the anthracene ring, with the 9th position being preferred. In the case of anthracene diether compounds, the substitution positions of the two ethers may be any two positions selected from the 10 substitution positions of the anthracene ring, with the 9th and 10th positions being preferred. Examples of anthracene diether compounds include anthracene-9,10-dibutyl ether and the like.

[0198] Examples of the substituted acyloxyanthracene compound include mono(substituted acyloxy)anthracene compounds and bis(substituted acyloxy)anthracene compounds, with bis(substituted acyloxy)anthracene compounds being preferred. In the case of mono(substituted acyloxy)anthracene compounds, the substitution position of the "substituted acyloxy" may be any one of the 1st, 2nd, and 9th positions on the anthracene ring, with the 9th position being preferred. In the case of bis(substituted acyloxy)anthracene compounds, the substitution positions of the two "substituted acyloxy" may be any two positions selected from the 10 substitution positions on the anthracene ring, with the 9th and 10th positions being preferred. Examples of the bis(substituted acyloxy)anthracene compound include 9,10-diacetyloxyanthracene and 9,10-bis(n-octanoyloxy)anthracene.

[0199] Examples of the alkoxycarbonyloxyanthracene compound include mono(alkoxycarbonyloxy)anthracene and bis(alkoxycarbonyloxy)anthracene, with bis(alkoxycarbonyloxy)anthracene compounds being preferred. In the case of mono(alkoxycarbonyloxy)anthraceneanthracene compounds, the substitution position of the "alkoxycarbonyloxy" may be any one of the 1st, 2nd, and 9th positions of the anthracene ring, with the 9th position being preferred. In the case of bis(alkoxycarbonyloxy)anthracene compounds, the substitution positions of the two "alkoxycarbonyloxy" may be any two positions selected from the 10 substitution positions of the anthracene ring, with the 9th and 10th positions being preferred.

[0200] Of these, as the component (E), anthracenes are preferred, substituted acyloxyanthracenes are more preferred, 9,10-bis(substituted acyloxy)anthracenes are even more preferred, and 9,10-bis(n-octanoyloxy)anthracene is particularly preferred.

[0201] In one embodiment of the present invention, the component (E) is preferably an anthracene, and more preferably a compound represented by the following formula (E-4), from the viewpoint of significantly achieving the effects of the present invention. [ka] (In formula (E-4), R 2e and R 3e each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 20 carbon atoms, an arylcarbonyl group having an aryl group having 4 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 20 carbon atoms, or an aryloxycarbonyl group having an aryl group having 4 to 20 carbon atoms. e and Y e each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

[0202] In formula (E-4), R 2e and R 3e each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 4 to 20 carbon atoms, an alkylcarbonyl group having an alkyl group having 1 to 20 carbon atoms, an arylcarbonyl group having an aryl group having 4 to 20 carbon atoms, an alkyloxycarbonyl group having an alkyl group having 1 to 20 carbon atoms, or an aryloxycarbonyl group having an aryl group having 4 to 20 carbon atoms.

[0203] R 2e and R 3e However, when R is an alkyl group or an aryl group, the compound represented by formula (E-4) is also called an "anthracene-9,10-diether compound." 2e and R 3e However, when R is an alkylcarbonyl group or an arylcarbonyl group, the compound represented by formula (E-4) is also called a "9,10-bis(substituted acyloxy)anthracene compound." 2e and R 3e However, when the group is an alkyloxycarbonyl group or an aryloxycarbonyl group, the compound represented by formula (E-4) is also called a "9,10-bis(alkoxycarbonyloxy)anthracene compound."

[0204] R 2e , R3e When is an alkyl group having 1 to 20 carbon atoms, the lower limit of the number of carbon atoms in the alkyl group is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more or 6 or more. The upper limit is preferably 15 or less, more preferably 12 or less, even more preferably 11 or less, and particularly preferably 10 or less or 9 or less. Examples of the alkyl group include linear, branched, and cyclic alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-amyl, i-amyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, and cyclohexyl, and an n-butyl or n-octyl group is preferred.

[0205] An aryl group is an aromatic group in which one hydrogen atom on the aromatic ring has been removed. 2e , R 3e When is an aryl group having 4 to 20 carbon atoms, the lower limit of the number of carbon atoms of the aryl group is preferably 5 or more, and more preferably 6 or more. The upper limit is preferably 18 or less, more preferably 12 or less, and even more preferably 10 or less. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a thienyl group, a pyrrolyl group, a furanyl group, a furyl group, a pyridyl group, a pyridazinyl group, a pyrimidyl group, a pyrazinyl group, a triazinyl group, a pyrrolidyl group, a piperidyl group, a quinolyl group, and an isoquinolyl group. A phenyl group, a naphthyl group, or an anthracenyl group is preferred, a phenyl group or a naphthyl group is more preferred, and a phenyl group is particularly preferred.

[0206] R 2e , R 3eHowever, in the case of an alkylcarbonyl group having an alkyl group of 1 to 20 carbon atoms, the lower limit of the number of carbon atoms in the alkyl group of the alkylcarbonyl group is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more or 6 or more. The upper limit is preferably 15 or less, more preferably 12 or less, even more preferably 11 or less, and particularly preferably 10 or less or 9 or less. Examples of the alkylcarbonyl group include an acetyl group, a propionyl group, an n-butanoyl group, an iso-butanoyl group, an n-pentanoyl group, an n-hexanoyl group, an n-heptanoyl group, an n-octanoyl group, a 2-ethylhexanoyl group, an n-nonanoyl group, an n-decanoyl group, and an n-dodecanoyl group, with an n-octanoyl group being preferred.

[0207] R 2e , R 3e However, in the case of an arylcarbonyl group having an aryl group having 4 to 20 carbon atoms, the lower limit of the number of carbon atoms in the aryl group of the arylcarbonyl group is preferably 5 or more, and more preferably 6 or more. The upper limit is preferably 18 or less, more preferably 12 or less, and even more preferably 10 or less. Examples of the arylcarbonyl group include a benzoyl group and a naphthoyl group, and a benzoyl group is preferred.

[0208] R 2e , R 3eHowever, in the case of an alkyloxycarbonyl group having an alkyl group of 1 to 20 carbon atoms, the lower limit of the number of carbon atoms in the alkyl group of the alkyloxycarbonyl group is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more or 6 or more. The upper limit is preferably 15 or less, more preferably 12 or less, even more preferably 11 or less, and particularly preferably 10 or less or 9 or less. Examples of the alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propyloxycarbonyl group, an isopropyloxycarbonyl group, an n-butoxycarbonyl group, an i-butoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an n-pentyloxycarbonyl group, a 2,2-dimethylpropyloxycarbonyl group, a cyclopentyloxycarbonyl group, an n-hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, an n-heptyloxycarbonyl group, a 2-methylpentyloxycarbonyl group, an n-octyloxycarbonyl group, and a 2-ethylhexyloxycarbonyl group. Examples of alkyloxycarbonyl groups include linear, branched, and cyclic alkyloxycarbonyl groups such as an alkyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, n-undecyloxycarbonyl group, n-dodecyloxycarbonyl group, n-tridecyloxycarbonyl group, n-tetradecyloxycarbonyl group, n-pentadecyloxycarbonyl group, n-hexadecyloxycarbonyl group, n-heptadecyloxycarbonyl group, n-octadecyloxycarbonyl group, n-nonadecyloxycarbonyl group, n-icosyloxycarbonyl group, and cyclohexyloxycarbonyl group, and the n-octyloxycarbonyl group is preferred.

[0209] R 2e , R 3eHowever, in the case of an aryloxycarbonyl group having an aryl group having 4 to 20 carbon atoms, the lower limit of the number of carbon atoms in the aryl group of the aryloxycarbonyl group is preferably 5 or more, and more preferably 6 or more. The upper limit is preferably 18 or less, more preferably 12 or less, and even more preferably 10 or less. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 3-phenanthryloxycarbonyl group, and a 2-anthryloxycarbonyl group, with the phenoxycarbonyl group being preferred.

[0210] In formula (E-4), X e and Y e each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. e and Y e The alkyl group in X preferably has 1 to 6 carbon atoms, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 1 or 2. e and Y e Examples of X include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-amyl group, an i-amyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and a 2-ethylhexyl group, of which a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, or a t-butyl group is preferred, a hydrogen atom, a methyl group, or an ethyl group is more preferred, a hydrogen atom or a methyl group is even more preferred, and a hydrogen atom is particularly preferred. e and Y e The substitution position may be any of the 1st to 8th positions of the anthracene ring.

[0211] Among these, the compound represented by formula (E-4) is preferably a compound represented by the following formula (E-4-1) or a compound represented by the following formula (E-4-2). [ka]

[0212] (E) Sensitizers that can be used include commercially available products such as "UVS-1331" and "UVS-581" manufactured by Air Water Performance Chemicals Inc.

[0213] Among the compounds represented by formula (E-4), an anthracene-9,10-diether compound can be produced by reacting a 9,10-dihydroxyanthracene compound with an etherifying agent. Among the compounds represented by formula (E-4), a 9,10-bis(substituted acyloxy)anthracene compound can be produced by reacting a 9,10-dihydroxyanthracene compound with an acylating agent in the presence of a basic compound. Among the compounds represented by formula (E-4), a 9,10-bis(alkoxycarbonyloxy)anthracene compound can be produced by reacting a 9,10-dihydroxyanthracene compound with a carbonate esterifying agent in the presence of a basic compound.

[0214] In one embodiment of the present invention, the component (E) is preferably a heterocycle, and more preferably a compound represented by the following formula (E-1), from the viewpoint of achieving the effects of the present invention more significantly. [ka] (In formula (E-1), R 1e represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxy group, a methoxy group, or a t-butoxy group.

[0215] R 1e represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxy group, a methoxy group, or a t-butoxy group. Examples of the linear or branched alkyl group having 1 to 7 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-butyl group. Among these, R 1e is preferably a hydrogen atom, a hydroxy group, a methoxy group, or a t-butoxy group, more preferably a hydrogen atom or a hydroxy group, and even more preferably a hydrogen atom.

[0216] R 1e The bonding position of may be any of the ortho-position, meta-position, and para-position based on the position of the phenylene group bonding to the nitrogen atom of mercaptotetrazole, but the para-position is preferred from the viewpoint of significantly obtaining the effects of the present invention.

[0217] The compound represented by formula (E-1) is preferably any compound selected from the group consisting of compounds represented by formula (E-2) below and compounds represented by formula (E-3) below. [ka]

[0218] When the photosensitive resin composition contains component (E), the content of component (E) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 1.5% by mass or more, based on 100% by mass of the nonvolatile components of the photosensitive resin composition, from the viewpoint of achieving significant effects of the present invention and appropriate photosensitivity. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less.

[0219] When the photosensitive resin composition contains the component (E), from the viewpoint of significantly achieving the effects of the present invention and obtaining appropriate photosensitivity, the mass ratio of the component (E) to the component (A) [component (E) / component (A)] is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and particularly preferably 0.015 or more. The upper limit is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.1 or less, and particularly preferably 0.05 or less or 0.03 or less.

[0220] When the photosensitive resin composition contains the component (B) and the component (E), from the viewpoint of significantly achieving the effects of the present invention and obtaining appropriate photosensitivity, the mass ratio of the component (E) to the component (B) [component (E) / component (B)] is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, particularly preferably 0.3 or more, 0.5 or more, or 0.8 or more. The upper limit is preferably 10 or less, more preferably 5 or less, even more preferably 3 or less, and particularly preferably 2 or less.

[0221] When the photosensitive resin composition contains the component (C) and the component (E), from the viewpoint of significantly achieving the effects of the present invention and obtaining appropriate photosensitivity, the mass ratio of the component (E) to the component (C) [component (E) / component (C)] is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.08 or more or 0.1 or more, and particularly preferably 0.15 or more. The upper limit is preferably 10 or less, more preferably 5 or less, even more preferably 1 or less, and particularly preferably 0.5 or less or 0.3 or less.

[0222] When the photosensitive resin composition contains the component (D) and the component (E), from the viewpoint of significantly achieving the effects of the present invention and obtaining appropriate photosensitivity, the lower limit of the mass ratio of the component (E) to the component (D) [component (E) / component (D)] is preferably at least 1, more preferably at least 3, even more preferably at least 5, and particularly preferably at least 8. The upper limit is preferably 1,000 or less, more preferably 100 or less, even more preferably 50 or less, and particularly preferably 40 or less, 30 or less, or 20 or less.

[0223] <(F) Surfactant> The photosensitive resin composition may contain a surfactant (F) as an optional component, and preferably contains a surfactant (F). By including the component (F) in the resin composition, a more uniform coating film can be formed when the resin composition is applied. The surfactant (F) may be used alone or in combination of two or more. Furthermore, the component (F) is a component different from the components (A) to (E).

[0224] Examples of the (F) surfactant include fluorine-based surfactants, silicone-based surfactants, polyether-based surfactants, poly(meth)acrylate-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, etc. Among these, polyether-based surfactants are preferred as the (F) component.

[0225] Examples of fluorosurfactants include fluorosurfactants composed of a compound having a fluoroalkyl group or a fluoroalkylene chain at least at any one of the terminal, main chain, and side chain. Specific examples include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol bis(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol bis(1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol bis(1,1,2,2-tetrafluorobutyl) ether, and hexapropylene glycol bis(1,1,2,2-tetrafluorobutyl) ether. Examples of such perfluoroalkyl esters include glycol bis(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, N-[3-(perfluorooctanesulfonamido)propyl]-N,N'-dimethyl-N-carboxymethyleneammonium betaine, perfluoroalkylsulfonamidopropyltrimethylammonium salts, perfluoroalkyl-N-ethylsulfonylglycine salts, bis(N-perfluorooctylsulfonyl-N-ethylaminoethyl)phosphate, and monoperfluoroalkylethyl phosphate esters.

[0226] Commercially available fluorine-based surfactants include "Megafac (registered trademark) F-142D", "Megafac (registered trademark) F-172", "Megafac (registered trademark) F-173", "Megafac (registered trademark) F-183", "Megafac (registered trademark) F-444", "Megafac (registered trademark) F-445", "Megafac (registered trademark) F-470", "Megafac (registered trademark) F-475", "Megafac (registered trademark) F-477", "Megafac (registered trademark) F-555", and "Megafac (registered trademark) F-559" (all trade names, manufactured by DIC Corporation), "Ftop (registered trademark) EF301", "Ftop (registered trademark) 303", and "Ftop (registered trademark) 352" (all trade names, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), "Florald (registered trademark) FC-430", "Florald (registered trademark) FC-431" (all trade names, manufactured by Sumitomo 3M Limited), and "Asahiguard (registered trademark) Examples of such polyolefin resins include "AG710" (trade name, manufactured by Asahi Glass Co., Ltd.), "Surflon (registered trademark) S-382", "Surflon (registered trademark) SC-101", "Surflon (registered trademark) SC-102", "Surflon (registered trademark) SC-103", "Surflon (registered trademark) SC-104", "Surflon (registered trademark) SC-105", and "Surflon (registered trademark) SC-106" (all trade names, manufactured by AGC Seimi Chemical Co., Ltd.), "BM-1000", "BM-1100" (all trade names, manufactured by Yusho Co., Ltd.), "NBX-15", "FTX-218", and "DFX-218" (all trade names, manufactured by Neos Corporation).

[0227] Commercially available silicone surfactants include, for example, "SH28PA," "SH7PA," "SH21PA," "SH30PA," and "ST94PA" (all trade names, manufactured by Dow Corning Toray Co., Ltd.), "BYK-301," "BYK-307," "BYK-331," "BYK-333," and "BYK-345" (all trade names, manufactured by BYK-Chemie Japan K.K.).

[0228] Commercially available polyether surfactants include, for example, "KP-341," "KP-360A," "KP-101," "KP-106," "KP-109," "KP-110," "KP-112," "KP-118," "KP-120," "KP-121," "KP-124," "KP-125," "KP-126," "KP-301," and "KP-306" (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), with "KP-341" being preferred.

[0229] When the photosensitive resin composition contains component (F), the content of component (F) is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more or 0.015% by mass or more, and particularly preferably 0.02% by mass or more, when the total components of the resin composition is taken as 100% by mass, from the viewpoint of forming a more uniform coating film when the resin composition is applied. The upper limit is preferably 1% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and particularly preferably 0.05% by mass or less.

[0230] When the photosensitive resin composition contains component (F), the content of component (F) is, from the viewpoint of forming a more uniform coating film when the resin composition is applied, preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more or 0.03% by mass or more, particularly preferably 0.05% by mass or more or 0.08% by mass or more, based on 100% by mass of the nonvolatile components of the resin composition. The upper limit is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, particularly preferably 0.3% by mass or less, 0.2% by mass or less, or 0.1% by mass or less.

[0231] When the photosensitive resin composition contains the component (F), from the viewpoint of forming a more uniform coating film when the resin composition is applied, the mass ratio of the component (F) to the component (A) [component (F) / component (A)] is preferably 0.0001 or more, more preferably 0.0005 or more, and even more preferably 0.0008 or more. The upper limit is preferably 0.1 or less, more preferably 0.01 or less, even more preferably 0.005 or less, and particularly preferably 0.002 or less.

[0232] When the photosensitive resin composition contains the component (B) and the component (F), from the viewpoint of forming a more uniform coating film when the resin composition is applied, the lower limit of the mass ratio of the component (F) to the component (B) [component (F) / component (B)] is preferably 0.005 or more, more preferably 0.01 or more, and even more preferably 0.02. The upper limit is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.1 or less, and particularly preferably 0.06 or less.

[0233] When the photosensitive resin composition contains the component (C) and the component (F), from the viewpoint of forming a more uniform coating film when the resin composition is applied, the mass ratio of the component (F) to the component (C) [component (F) / component (C)] is preferably 0.0005 or more, more preferably 0.001 or more, even more preferably 0.005 or more, and particularly preferably 0.01 or more. The upper limit is preferably 0.1 or less, more preferably 0.05 or less, even more preferably 0.03 or less, and particularly preferably 0.02 or less.

[0234] When the photosensitive resin composition contains the component (D) and the component (F), from the viewpoint of forming a more uniform coating film when the resin composition is applied, the mass ratio of the component (F) to the component (D) [component (F) / component (D)] is preferably at least 0.01 or at least 0.05, more preferably at least 0.1, even more preferably at least 0.2, and particularly preferably at least 0.4. The upper limit is preferably at most 100, more preferably at most 10, even more preferably at most 5, and particularly preferably at most 1 or at most 0.8.

[0235] When the photosensitive resin composition contains the component (E) and the component (F), from the viewpoint of forming a more uniform coating film when the resin composition is applied, the mass ratio of the component (F) to the component (E) [component (F) / component (E)] is preferably 0.001 or more or 0.005 or more, more preferably 0.01 or more, even more preferably 0.02 or more, and particularly preferably 0.04 or more. The upper limit is preferably 5 or less, more preferably 1 or less, even more preferably 0.5 or less, and particularly preferably 0.1 or less or 0.08 or less.

[0236] <(G) Solvent> The photosensitive resin composition may contain a solvent (G) as an optional component. The solvent (G) is a volatile component that can dissolve at least one of the components (A) to (F) and the component (H). The component (G) may be used alone or in combination of two or more.

[0237] Examples of component (B) include solvents composed of atoms selected from carbon, oxygen, nitrogen, phosphorus, sulfur, halogen, and hydrogen atoms. From the viewpoint of safety, component (G) is preferably a solvent composed of atoms selected from carbon, oxygen, and hydrogen atoms, and more preferably a solvent composed of carbon, oxygen, and hydrogen atoms.

[0238] Examples of component (G) include glycol-based organic solvents, glycol ether-based organic solvents, glycol ether ester-based organic solvents, ketone-based organic solvents, ester-based organic solvents, ether-based organic solvents, alcohol-based organic solvents, aliphatic hydrocarbon-based organic solvents, aromatic organic solvents, nitrogen-based organic solvents, sulfur-based organic solvents, and halogen-based organic solvents. Examples of nitrogen-based organic solvents include amide-based organic solvents, urea-based organic solvents, and nitrile-based organic solvents. From the viewpoint of safety, component (G) is preferably an ester-based organic solvent, ketone-based organic solvent, glycol-based organic solvent, glycol ether-based organic solvent, or glycol ether ester-based organic solvent, more preferably an ester-based organic solvent or ketone-based organic solvent, and particularly preferably a ketone-based organic solvent.

[0239] Examples of glycol-based organic solvents include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and trimethylene glycol.

[0240] Examples of glycol ether organic solvents include cellosolves such as ethylene glycol monomethyl ether (also known as methyl cellosolve), ethylene glycol monoethyl ether (also known as cellosolve), ethylene glycol monopropyl ether (also known as propyl cellosolve), ethylene glycol monobutyl ether (also known as butyl cellosolve), ethylene glycol monoisobutyl ether (also known as isobutyl cellosolve), ethylene glycol mono-tert-butyl ether (also known as tert-butyl cellosolve), and ethylene glycol monohexyl ether; diethylene glycol monomethyl ether (also known as methyl carbitol), diethylene glycol monoethyl ether ( carbitols such as diethylene glycol monopropyl ether (also known as propyl carbitol) and diethylene glycol monobutyl ether (DB) (also known as butyl carbitol); propylene glycol ethers such as propylene glycol monomethyl ether (PGM), propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; and dipropylene glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether.

[0241] Examples of glycol ether ester organic solvents include cellosolve esters such as ethylene glycol monomethyl ether acetate (also known as methyl cellosolve acetate), ethylene glycol monoethyl ether acetate (also known as cellosolve acetate), and ethylene glycol monobutyl ether acetate (also known as butyl cellosolve acetate); carbitol esters such as diethylene glycol monoethyl ether acetate (EDGAc) (also known as carbitol acetate) and diethylene glycol monobutyl ether acetate (also known as butyl carbitol acetate); propylene glycol ether esters such as propylene glycol monomethyl ether acetate (PGMEAc) and propylene glycol monoethyl ether acetate; and dipropylene glycol ether esters such as dipropylene glycol monomethyl ether acetate.

[0242] Examples of ketone-based organic solvents include aliphatic acyclic ketones such as acetone, methyl ethyl ketone (MEK), diethyl ketone, 2-pentanone, methyl isobutyl ketone, 2-hexanone, 2-heptanone (MAK), and diisobutyl ketone; aliphatic cyclic ketones such as cyclopentanone, cyclohexanone (Anone), and 2-methylcyclohexanone; and aromatic ketones such as acetophenone. The lower limit of the number of carbon atoms in the ketone-based organic solvent is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. The upper limit of the number of carbon atoms in the ketone-based organic solvent is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

[0243] Ester-based organic solvents are organic solvents having an ester structure that do not fall under the category of glycol ether ester-based organic solvents. Examples include fatty acid alkyl esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, n-pentyl acetate, isopentyl acetate, ethyl propionate, propyl propionate, and isopropyl propionate; hydroxy acid alkyl esters such as methyl lactate, ethyl lactate, and butyl lactate; keto acid alkyl esters such as methyl acetoacetate and ethyl acetoacetate; lactones such as γ-butyrolactone and α-acetyl-γ-butyrolactone; and aromatic esters such as methyl benzoate and ethyl benzoate. Lactones are preferred as ester-based organic solvents. Furthermore, the number of carbon atoms in the ester-based organic solvent is preferably 3 to 9.

[0244] The ether-based organic solvent is an organic solvent having an ether structure that does not fall under the category of glycol ether-based organic solvents or glycol ether ester-based organic solvents, and examples thereof include aliphatic acyclic ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; aliphatic cyclic ethers such as tetrahydrofuran, 1,4-dioxane, and 1,3-dioxolane; and aromatic ethers such as anisole and phenetole. The number of carbon atoms in the ether-based organic solvent is preferably 2 to 9.

[0245] Alcohol-based organic solvents are organic solvents having an alcohol structure that does not fall under the category of glycol-based organic solvents and glycol ether-based organic solvents, and examples thereof include aliphatic acyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, isopentyl alcohol, sec-pentyl alcohol, tert-pentyl alcohol, neopentyl alcohol, n-hexyl alcohol, n-heptyl alcohol, isoheptyl alcohol, n-octyl alcohol, and 2-ethylhexyl alcohol; aliphatic cyclic alcohols such as cyclohexanol; and aromatic alcohols such as benzyl alcohol and phenethyl alcohol.

[0246] Examples of aliphatic hydrocarbon organic solvents include n-pentane, n-hexane, 2-methylpentane (also known as isohexane), n-heptane, n-octane, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin, etc. The aliphatic hydrocarbon organic solvent preferably has 5 to 10 carbon atoms.

[0247] Examples of aromatic organic solvents include C benzene, toluene, o-xylene, m-xylene, p-xylene, and ethylbenzene. 6-8 Aromatic hydrocarbons: C9 aromatic hydrocarbons such as 1,2,3-trimethylbenzene, 1,3,5-trimethylbenzene (also known as mesitylene), 1,2,4-trimethylbenzene, 4-ethyltoluene, 3-ethyltoluene, and 2-ethyltoluene; C1 aromatic hydrocarbons such as 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, 3-ethyl-o-xylene, 4-ethyl-o-xylene, 2-ethyl-p-xylene, 1,2,3,5-tetramethylbenzene, and tetralin. 10 Examples include aromatic hydrocarbons and aromatic heterocyclic compounds such as pyridine, furan, thiophene, etc. The aromatic organic solvent preferably has 6 to 10 carbon atoms.

[0248] Examples of amide-based organic solvents include aliphatic acyclic amides such as N,N-dimethylacetamide and N,N-dimethylformamide, lactams such as N-methyl-2-pyrrolidone and N-cyclohexyl-2-pyrrolidone, and phosphoric acid amides such as hexamethylphosphoramide. The number of carbon atoms in the amide-based organic solvent is preferably 2 to 10.

[0249] Examples of urea-based organic solvents include tetramethylurea and 1,3-dimethyl-2-imidazolinone.

[0250] Examples of the nitrile organic solvent include acetonitrile, propionitrile, benzonitrile, etc. The nitrile organic solvent preferably has 2 to 10 carbon atoms.

[0251] An example of the sulfur-based organic solvent is dimethyl sulfoxide.

[0252] Examples of halogen-based organic solvents include chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, etc. The halogen-based organic solvent preferably has 1 to 10 carbon atoms.

[0253] Among these, γ-butyrolactone, cyclopentanone, cyclohexanone, propylene glycol, or propylene glycol monomethyl ether acetate is preferred, cyclohexanone or γ-butyrolactone is more preferred, and cyclohexanone is even more preferred.

[0254] When the photosensitive resin composition contains component (G), the content of component (G) may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, etc., based on 100% by mass of the entire photosensitive resin composition. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less. By keeping the content of component (G) within the above range, the photosensitive resin composition can be made into a varnish with an appropriate viscosity.

[0255] When the photosensitive resin composition contains component (G), from the viewpoint of obtaining a varnish with an appropriate viscosity, the lower limit of the mass ratio of component (G) to component (A) [component (G) / component (A)] is preferably 0.1 or more or 0.5 or more, more preferably 1 or more, even more preferably 1.5 or more, and particularly preferably 2 or more or 2.5 or more. The upper limit is preferably 10 or less, more preferably 8 or less, even more preferably 5 or less, and particularly preferably 4 or less or 3 or less.

[0256] <(H) Other Additives> The photosensitive resin composition may further contain (H) other additives to the extent that the object of the present invention is not impaired. Examples of (H) other additives include thermoplastic resins; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black; polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as bentone and montmorillonite; silicone-based, fluorine-based, and vinyl resin-based antifoaming agents; flame retardants such as epoxy resins, antimony compounds, phosphorus-based compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters; and thermosetting resins such as phenolic curing agents and cyanate ester-based curing agents. Furthermore, the components (A) to (G) may also function as thermoplastic resins, colorants, polymerization inhibitors, thickeners, antifoaming agents, flame retardants, or curing agents. In this case, the component in question is considered to be one of components (A) to (G), not component (H).

[0257] [Method for producing photosensitive resin composition] The photosensitive resin composition can be produced by appropriately mixing the above-mentioned component (A) as an essential component with the above-mentioned components (B) to (H) as optional components, and kneading or stirring the mixture, if necessary, using a kneading means such as a triple roll mill, ball mill, bead mill, or sand mill, or a stirring means such as a super mixer or planetary mixer.

[0258] [Physical properties and applications of photosensitive resin compositions] In one embodiment, the photosensitive resin composition exhibits excellent limiting resolution. For example, exposure and development are performed using a mask that draws circular holes (vias) with opening diameters of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm in the exposure pattern. In this case, the limiting resolution, which is the minimum size that can be opened, is preferably 30 μm or less or 25 μm or less, more preferably 20 μm or less, even more preferably 15 μm or less or 10 μm or less, and particularly preferably 9 μm or less, 8 μm or less, 7 μm or less, 6 μm or less, or 5 μm or less. The limiting resolution can be evaluated according to the method described in the Examples below.

[0259] In one embodiment, the photosensitive resin composition exhibits the property of being developable with an alkaline aqueous solution at room temperature in a short time. Examples of alkaline aqueous solutions used as the developer include aqueous solutions of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; and aqueous solutions of bases that do not contain metal ions, such as tetraalkylammonium hydroxide (TMAH). From the viewpoint of not containing metal ions and not adversely affecting semiconductor chips, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred. The temperature during development is preferably 40°C or less, more preferably 35°C or less, even more preferably 30°C or less, and particularly preferably 25°C or less. The lower limit of the temperature during development is not particularly limited, but may be 0°C or more, 5°C or more, 10°C or more, 15°C or more, or 20°C or more. Furthermore, the temperature during development is preferably room temperature. From the viewpoint of shortening the production time, the development time is preferably 600 seconds or less, more preferably 300 seconds or less, even more preferably 240 seconds or less or 200 seconds or less, and particularly preferably 180 seconds or less, 160 seconds or less, or 140 seconds or less. From the viewpoint of suppressing the variation in resolution between lots, the lower limit of the development time is preferably 15 seconds or more, more preferably 30 seconds or more, and even more preferably 60 seconds or more.

[0260] In one embodiment, a cured product obtained by thermally curing the photosensitive resin composition at 160°C for 120 minutes exhibits the characteristic of a low dielectric constant (Dk). The dielectric constant is preferably 4 or less or 3.5 or less, more preferably 3.2 or less, 3.1 or less or 3 or less, and even more preferably 2.9 or less or 2.8 or less. The lower limit is not particularly limited, but may be 0.01 or more, 0.1 or more, 1 or more, etc. The dielectric constant can be measured according to the method described in the examples below.

[0261] In one embodiment, a cured product obtained by thermally curing the photosensitive resin composition at 160°C for 120 minutes exhibits the characteristic of a low dielectric loss tangent (Df). The dielectric loss tangent is preferably 0.03 or less or 0.025 or less, more preferably 0.02 or less or 0.015 or less, and even more preferably 0.01 or less. The lower limit is not particularly limited, but may be 0.0005 or more or 0.001 or more. The dielectric loss tangent can be measured according to the method described in the examples below.

[0262] In one embodiment, a cured product obtained by thermally curing a photosensitive resin composition at 160°C for 120 minutes exhibits the characteristic of a low coefficient of linear thermal expansion (CTE). The coefficient of linear thermal expansion (ppm / °C) in the planar direction in the range of 25°C to 150°C is preferably 70 ppm / °C or less, more preferably 65 ppm / °C or less, even more preferably 60 ppm / °C or less or 50 ppm / °C or less, and particularly preferably 45 ppm / °C or less. The lower limit is not particularly limited, but may be 1 ppm / °C or more, 10 ppm / °C or more, etc. The coefficient of linear thermal expansion can be measured according to the method described in the Examples below.

[0263] In one embodiment, a cured product obtained by thermally curing a photosensitive resin composition at 160°C for 120 minutes exhibits the characteristic of a high glass transition temperature (Tg). The glass transition temperature is preferably 175°C or higher, more preferably 180°C or higher or 185°C or higher, even more preferably 190°C or higher or 195°C or higher, and particularly preferably 200°C or higher, 205°C or higher, or 210°C or higher. The upper limit is not particularly limited, but may be 400°C or lower, 300°C or lower, etc. The glass transition temperature can be measured according to the method described in the examples below.

[0264] In one embodiment, a cured product obtained by thermally curing a photosensitive resin composition at 160°C for 120 minutes exhibits a high elastic modulus. The elastic modulus at 25°C is preferably 1.6 GPa or more or 1.8 GPa or more, more preferably 2.0 GPa or more or 2.2 GPa or more, even more preferably 2.4 GPa or more, and particularly preferably 2.5 GPa or more. The upper limit is not particularly limited, but may be 50 GPa or less or 10 GPa or less, for example. The elastic modulus can be measured according to the method described in the Examples below.

[0265] In one embodiment, a cured product obtained by thermally curing a photosensitive resin composition at 160°C for 120 minutes exhibits a high elongation at break. The elongation at break at 25°C is preferably 25% or more, more preferably 30% or more, 35% or more, or 40% or more, even more preferably 45% or more or 50% or more, and particularly preferably 55% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100% or more. The upper limit is not particularly limited, but may be 300% or less, 200% or less, etc. The elongation at break can be measured according to the method described in the Examples below.

[0266] The use of the photosensitive resin composition of the present invention is not particularly limited, and it can be used in a wide range of applications where photosensitive resin compositions are used, such as a photosensitive film with a support, an insulating resin sheet such as a prepreg, a silicon wafer, a circuit board (for laminate boards, multilayer printed wiring boards, etc.), a solder resist, a buffer coating film, an underfill material, a die bonding material, a semiconductor encapsulant, a hole filling resin, and a component embedding resin. Among these, photosensitive resin compositions for insulating layers of printed wiring boards (printed wiring boards in which a cured product of the photosensitive resin composition is used as an insulating layer), photosensitive resin compositions for interlayer insulating layers (printed wiring boards in which a cured product of the photosensitive resin composition is used as an interlayer insulating layer), photosensitive resin compositions for plating formation (printed wiring boards in which plating is formed on a cured product of the photosensitive resin composition), photosensitive resin compositions for solder resists (printed wiring boards in which a cured product of the photosensitive resin composition is used as a solder resist), photosensitive resin compositions for rewiring formation layers of wafer-level packages (wafer-level packages in which a cured product of the photosensitive resin composition is used as a rewiring formation layer), and the like. The photosensitive resin composition can be suitably used as a photosensitive resin composition for a rewiring formation layer in a fan-out wafer level package (a fan-out wafer level package in which a cured product of the photosensitive resin composition serves as a rewiring formation layer), a photosensitive resin composition for a rewiring formation layer in a fan-out panel level package (a fan-out panel level package in which a cured product of the photosensitive resin composition serves as a rewiring formation layer), a photosensitive resin composition for a buffer coat (a semiconductor device in which a cured product of the photosensitive resin composition serves as a buffer coat), and a photosensitive resin composition for an insulating layer in a display (a display in which a cured product of the photosensitive resin composition serves as an insulating layer).

[0267] [Photosensitive film] The photosensitive resin composition of the present invention can be applied to a photosensitive film. The photosensitive film can include a support and a photosensitive resin composition layer formed on the support. The photosensitive resin composition layer is a layer made of the above-mentioned photosensitive resin composition. The photosensitive film may also include a support, a photosensitive resin composition layer, and a protective film in this order.

[0268] Examples of the support include polyethylene terephthalate (PET) film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, and triacetyl acetate film, with polyethylene terephthalate film being particularly preferred.

[0269] Examples of commercially available supports include products manufactured by Oji Paper Co., Ltd. under the product names "Alphan MA-410" and "E-200C," products manufactured by Tamapoly Corporation under the product names "GF-1" and "GF-8," polypropylene films manufactured by Shin-Etsu Film Co., Ltd., the PS series manufactured by Teijin Limited under the product name "PS-25," and polyethylene terephthalate films manufactured by Toray Industries, Inc. under the product name "Lumirror T6AM."

[0270] The support may also be a support with a release layer, which has a release layer on the surface that bonds to the resin composition layer. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available release agents include "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation. The support with a release layer may also be a commercially available product, such as "Lumirror T60" and "Lumirror R80" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, or "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0271] The thickness of the support is preferably in the range of 5 μm to 100 μm, and more preferably in the range of 10 μm to 50 μm.

[0272] The thickness of the photosensitive resin composition layer is not particularly limited and may be, for example, 1 μm or more and 100 μm or less, and is preferably 2 μm or more, more preferably 4 μm or more, and is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less.

[0273] The photosensitive resin composition layer may be protected by a protective film. Protecting the photosensitive resin composition layer with a protective film can prevent dust from adhering to the surface of the photosensitive resin composition layer and scratches. The protective film may be made of the same material as the support. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. The protective film is preferably one in which the adhesive strength between the photosensitive resin composition layer and the protective film is smaller than the adhesive strength between the photosensitive resin composition layer and the support.

[0274] An example of a commercially available protective film is "MA-411" (biaxially oriented polypropylene film) manufactured by Oji F-Tex Co., Ltd.

[0275] The photosensitive film can be produced, for example, by applying the photosensitive resin composition onto a support using a die coater or the like, and then drying off the (G) solvent as necessary.

[0276] Drying may be carried out by known methods such as heating, hot air blowing, etc. The drying conditions are not particularly limited, but drying is carried out so that the content of the solvent in the resin composition layer is preferably 10% by mass or less, more preferably 5% by mass or less.

[0277] [Semiconductor package substrate and its manufacturing method] The semiconductor package substrate of the present invention includes an insulating layer formed from a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a rewiring formation layer, an interlayer insulating layer, a buffer coating film, or a solder resist.

[0278] In particular, the semiconductor package substrate of the first embodiment of the present invention can be manufactured using the above-mentioned photosensitive resin composition, and the cured product of the photosensitive resin composition is used as an insulating layer. Specifically, the manufacturing method of the semiconductor package substrate of the first embodiment includes: (I) forming a photosensitive resin composition layer containing the photosensitive resin composition of the present invention on a circuit board; (II) a step of irradiating the photosensitive resin composition layer with actinic rays; and (III) Step of developing the photosensitive resin composition layer The method for manufacturing a semiconductor package substrate preferably includes steps (I) to (III) in the order of step (I), step (II), and step (III).

[0279] <Process (I)> In step (I), a photosensitive resin composition layer containing the photosensitive resin composition of the present invention is formed on a circuit board. Examples of a method for forming the photosensitive resin composition layer include a method in which a resin varnish containing the photosensitive resin composition is directly applied onto the circuit board.

[0280] When a resin varnish containing a photosensitive resin composition is applied directly onto a circuit board, a photosensitive resin composition layer can be formed on the circuit board by drying and volatilizing the (G) solvent.

[0281] Examples of resin varnish application methods include gravure coating, microgravure coating, reverse coating, kiss reverse coating, die coating, slot die coating, lip coating, comma coating, blade coating, roll coating, knife coating, curtain coating, chamber gravure coating, slot orifice coating, spin coating, slit coating, spray coating, dip coating, hot melt coating, bar coating, applicator coating, air knife coating, curtain flow coating, offset printing, brush coating, and full-surface printing using screen printing.

[0282] The resin varnish may be applied in several batches, in one application, or by a combination of several different methods. Among these, the die coating method is preferred because it provides excellent uniformity. Furthermore, to avoid contamination, it is preferable to carry out the application process in an environment where foreign matter is less likely to be generated, such as a clean room.

[0283] After the resin varnish is applied, it is dried, if necessary, in a hot air oven or far-infrared oven. The drying conditions are preferably 80°C to 120°C for 3 to 13 minutes. In this way, a photosensitive resin composition layer is formed on the circuit board.

[0284] Examples of circuit boards include glass epoxy boards, metal boards, polyester boards, polyimide boards, BT resin boards, and thermosetting polyphenylene ether boards. Here, the term "circuit board" refers to a board in which a patterned conductor layer (circuit) is formed on one or both sides of a support substrate such as those described above. Also included in the term "circuit board" is a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits). The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

[0285] <Process (II)> In step (II), the photosensitive resin composition layer is irradiated with actinic rays. In step (II), it is preferable to irradiate the photosensitive resin composition layer with actinic rays after the photosensitive resin composition layer is provided on the circuit board in step (I). It is also preferable to carry out an exposure step in which actinic rays are irradiated to predetermined portions of the photosensitive resin composition layer through a mask pattern. Examples of actinic rays include ultraviolet rays, visible rays, electron beams, and X-rays, with ultraviolet rays being particularly preferred. The irradiation dose of ultraviolet rays is 10 mJ / cm. 2 ~1000mJ / cm 2 The exposure method includes a contact exposure method in which a mask pattern is brought into close contact with the circuit board, and a non-contact exposure method in which exposure is carried out using parallel light without contact, and either method may be used.

[0286] In step (II), vias can be formed using a via pattern such as a round hole pattern as the mask pattern. The via diameter (opening diameter) is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 30 μm or less, and particularly preferably 25 μm or less, 20 μm or less, 15 μm or less, 10 μm or less, 9 μm or less, 8 μm or less, 7 μm or less, 6 μm or less, or 5 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more, 0.5 μm or more, etc.

[0287] <Process (III)> In step (III), the photosensitive resin composition layer is developed. After step (II), a development step is performed in which unexposed portions of the photosensitive resin composition layer are removed with a developer, thereby forming a pattern. Development is preferably performed by wet development.

[0288] In the case of the wet development, a stable and easy-to-use developer such as an alkaline solution, an aqueous developer, or an organic solvent can be used. Examples of alkaline solutions include an alkaline aqueous solution. The developer is preferably an alkaline aqueous solution or an organic solvent, with an alkaline aqueous solution being more preferred from the viewpoint of safety, and an organic solvent being more preferred from the viewpoint of improving developability (efficiently removing the unexposed portions of the photosensitive resin composition layer). Since the photosensitive resin composition of the present invention can be developed with an alkaline aqueous solution, it is preferable to use an alkaline aqueous solution as the developer from the viewpoint of safety, but an organic solvent may also be used as the developer. Furthermore, known methods such as spraying, swing immersion, brushing, and scraping may be appropriately employed as the development method.

[0289] Examples of alkaline aqueous solutions used as the developer include aqueous solutions of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; and aqueous solutions of bases that do not contain metal ions, such as tetraalkylammonium hydroxide (TMAH). From the viewpoint of not containing metal ions and not affecting semiconductor chips, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred.

[0290] These alkaline aqueous solutions may contain surfactants, antifoaming agents, etc. to improve the development effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8 to 12, more preferably in the range of 9 to 11. The base concentration of the alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected depending on the developability of the photosensitive resin composition layer, but is preferably 50°C or less or 40°C or less, more preferably 35°C or less, even more preferably 30°C or less, and particularly preferably 25°C or less. There is no particular restriction on the lower limit of the temperature during development, but it may be 0°C or more, 5°C or more, 10°C or more, 15°C or more, 20°C or more, etc.

[0291] Examples of organic solvents used as developers include acetone, ethyl acetate, alkoxyethanols having an alkoxy group with 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether (PGME).

[0292] The concentration of such an organic solvent is preferably 2% by mass to 90% by mass based on the total amount of the developer. The temperature of such an organic solvent can be adjusted according to the developability. Such organic solvents can be used alone or in combination of two or more. Examples of organic solvent-based developers that can be used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0293] In forming a pattern, two or more development methods may be used in combination as needed. Development methods include dipping, bathing, spraying, high-pressure spraying, brushing, and slapping, with the high-pressure spraying method being preferred for improving resolution. When using a spraying method, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0294] After development, the resist may be rinsed with an organic solvent, such as propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME). A preferred rinse method is a spray method.

[0295] <Thermal curing (post-bake) process> After completion of the above step (III), a thermal curing (post-baking) step may be performed as necessary. Although the curing of the photosensitive resin composition layer may proceed in the above steps (I) to (III), the thermal curing step can further promote the curing of the photosensitive resin composition layer, thereby obtaining an insulating layer with superior mechanical strength. Examples of the post-baking step include a heating step using a clean oven. The thermal curing atmosphere may be an air atmosphere or an inert gas atmosphere such as nitrogen. The heating conditions may be appropriately selected depending on the type and content of the resin component in the photosensitive resin composition. The heating temperature is preferably 150°C to 250°C, more preferably 150°C to 170°C. Since the photosensitive resin composition of the present invention contains a polyimide polymer, it can be cured at a low temperature. The heating time is preferably 20 to 240 minutes, more preferably 30 to 180 minutes.

[0296] <Other processes> The method for manufacturing a semiconductor package substrate according to the first embodiment may further include a drilling step and a desmearing step after forming an insulating layer as a cured photosensitive resin composition layer. These steps may be performed according to various methods used in manufacturing semiconductor package substrates and known to those skilled in the art.

[0297] After forming the insulating layer, if desired, via holes or through holes may be formed in the insulating layer formed on the circuit board by a drilling process. The drilling process can be performed by a known method such as a drill, a laser, or plasma, or by a combination of these methods as needed, but a drilling process using a laser such as a carbon dioxide laser or a YAG laser is preferred.

[0298] The desmearing step is a step of performing a desmear treatment. Generally, resin residue (smear) adheres to the inside of the opening formed in the drilling step. Since such smear can cause poor electrical connection, it is preferable to perform a treatment to remove the smear (desmearing treatment) in this step.

[0299] The desmearing treatment may be performed by a dry desmearing treatment, a wet desmearing treatment, or a combination thereof.

[0300] An example of the dry desmear treatment is a desmear treatment using plasma. The desmear treatment using plasma can be performed using a commercially available plasma desmear treatment apparatus. Among the commercially available plasma desmear treatment apparatuses, examples suitable for use in manufacturing semiconductor package substrates include a microwave plasma apparatus manufactured by Nissin Corporation and an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd.

[0301] Examples of wet desmear treatments include desmear treatments using an oxidizing agent solution. When desmear treatments are performed using an oxidizing agent solution, it is preferable to perform a swelling treatment using a swelling solution, an oxidation treatment using an oxidizing agent solution, and a neutralization treatment using a neutralizing solution in this order. Examples of swelling solutions include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing a substrate having via holes or the like formed therein in a swelling solution heated to 60°C to 80°C for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganate aqueous solution, such as a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous sodium hydroxide solution. The oxidation treatment using an oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Commercially available alkaline permanganate aqueous solutions include, for example, "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. The neutralization treatment using a neutralizing solution is preferably carried out by immersing the substrate after oxidation treatment in the neutralizing solution at 30°C to 50°C for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and a commercially available product thereof is, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan.

[0302] When the dry desmear treatment and the wet desmear treatment are performed in combination, the dry desmear treatment may be performed first, or the wet desmear treatment may be performed first.

[0303] In any case where the insulating layer is formed as a rewiring formation layer, an interlayer insulating layer, or a solder resist, a drilling step and a desmearing step may be performed after the thermal curing step. In addition, in the manufacturing method of a semiconductor package substrate, a plating step may be further performed.

[0304] The plating process is a process of forming a conductor layer on an insulating layer. Examples of methods for forming the conductor layer include a method of forming the conductor layer by sputtering after forming the insulating layer, a method of forming the conductor layer by combining electroless plating and electrolytic plating, and a method of forming a plating resist with a reverse pattern to the conductor layer and then forming the conductor layer by electroless plating alone. Subsequent pattern formation methods that can be used include, for example, subtractive methods and semi-additive methods.

[0305] The semiconductor package substrate of the second embodiment of the present invention can be manufactured using the above-mentioned photosensitive resin composition, and the cured product of the photosensitive resin composition is used as a rewiring formation layer. Specifically, the manufacturing method of the semiconductor package substrate of the second embodiment includes the following steps: (A) a step of laminating a temporary fixing film on a substrate; (B) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (C) forming an encapsulation layer on the semiconductor chip; (D) peeling the substrate and the temporary fixing film from the semiconductor chip; (E) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; (F) forming a rewiring layer as a conductor layer on the rewiring formation layer; and (G) forming a solder resist layer on the rewiring layer; The method for manufacturing a semiconductor package substrate according to the second embodiment includes: (H) A process of dicing and separating multiple semiconductor package substrates into individual semiconductor package substrates. may also include:

[0306] <Process (A)> Step (A) is a step of laminating a temporary fixing film on a substrate. The lamination conditions for the substrate and the temporary fixing film are not particularly limited, but for example, the pressure-bonding temperature (lamination temperature) is preferably 70°C to 140°C, and the pressure-bonding pressure is preferably 1 kgf / cm. 2 ~11kgf / cm 2 The pressure bonding time is preferably 5 to 300 seconds, and lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg or less. The lamination process may be a batch process or a continuous process using rolls. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nikko Materials Co., Ltd., a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a roll-type dry coater manufactured by Hitachi Industries Co., Ltd., and a vacuum laminator manufactured by Hitachi AIC Corporation.

[0307] Examples of the substrate include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates such as FR-4 substrates in which glass fibers are impregnated with epoxy resin or the like and then thermoset; and substrates made of bismaleimide triazine resins such as BT resin.

[0308] The temporary fixing film may be made of any material that can be peeled off from the semiconductor chip and can temporarily fix the semiconductor chip. Commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

[0309] <Process (B)> Step (B) is a step of temporarily fixing semiconductor chips on a temporary fixing film. Temporarily fixing semiconductor chips can be performed using a device such as a flip chip bonder or a die bonder. The layout and number of semiconductor chips can be appropriately set depending on the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, and the like. For example, the semiconductor chips may be temporarily fixed by arranging them in a matrix of multiple rows and multiple columns.

[0310] <Process (C)> Step (C) is a step of forming an encapsulating layer on the semiconductor chip. Any insulating material can be used for the encapsulating layer, and the above-mentioned photosensitive resin composition may also be used. The encapsulating layer is usually formed by a method including a step of forming an encapsulating resin composition layer on the semiconductor chip and a step of thermally curing this resin composition layer to form the encapsulating layer.

[0311] The encapsulating resin composition layer is preferably formed by a compression molding method, in which a semiconductor chip and the encapsulating resin composition are typically placed in a mold, and pressure and, if necessary, heat are applied to the encapsulating resin composition in the mold to form an encapsulating resin composition layer that covers the semiconductor chip.

[0312] Specific operations of the compression molding method can be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. An encapsulating resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip to which the encapsulating resin composition has been applied is attached to the lower mold together with the substrate and the temporary fixing film. Thereafter, the upper and lower molds are clamped together, and heat and pressure are applied to the encapsulating resin composition to perform compression molding.

[0313] Furthermore, specific operations of the compression molding method may be, for example, as follows: An upper mold and a lower mold are prepared as molds for compression molding. An encapsulating resin composition is placed on the lower mold. A semiconductor chip is attached to the upper mold together with a substrate and a temporary fixing film. Thereafter, the upper and lower molds are clamped together so that the encapsulating resin composition placed on the lower mold contacts the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

[0314] The molding conditions vary depending on the composition of the encapsulating resin composition, and appropriate conditions can be adopted to achieve good encapsulation. For example, the mold temperature during molding is preferably a temperature at which the encapsulating resin composition exhibits excellent compression moldability, and is preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 120°C or higher, and preferably 200°C or lower, more preferably 170°C or lower, and particularly preferably 150°C or lower. The pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, and preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The cure time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 5 minutes or longer, and preferably 60 minutes or shorter, more preferably 30 minutes or shorter, and particularly preferably 20 minutes or shorter. Typically, the mold is removed after the encapsulating resin composition layer is formed. The mold may be removed before or after the encapsulating resin composition layer is thermally cured.

[0315] The compression molding method may be carried out by discharging the encapsulating resin composition filled in a cartridge into a lower mold.

[0316] <Process (D)> Step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor chip. It is desirable to adopt an appropriate peeling method depending on the material of the temporary fixing film. Examples of peeling methods include a method in which the temporary fixing film is heated, foamed, or expanded to peel it off. Another example of a peeling method is a method in which the temporary fixing film is irradiated with ultraviolet light through the substrate to reduce the adhesive strength of the temporary fixing film, thereby peeling it off.

[0317] In the method of peeling off the temporary fixing film by heating, foaming or expanding it, the heating temperature is preferably 100° C. to 250° C. The heating time is preferably 1 second to 15 minutes, and may be, for example, a relatively short time such as 1 second to 90 seconds, or a relatively long time such as 5 minutes to 15 minutes. In the method of peeling off the temporary fixing film by irradiating it with ultraviolet light to reduce the adhesive strength of the temporary fixing film, the irradiation dose of ultraviolet light is 10 mJ / cm. 2 ~1000mJ / cm 2 is preferred.

[0318] <Process (E)> Step (E) is a step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off. The rewiring formation layer uses the photosensitive resin composition of the present invention. The method for forming the rewiring formation layer is the same as the method for forming the photosensitive resin composition layer in step (I) in the first embodiment.

[0319] When forming the rewiring formation layer, via holes may be formed in the rewiring formation layer to connect the semiconductor chip and the rewiring layer to each other.

[0320] The via hole can usually be formed by performing an exposure step in which the surface of the photosensitive resin composition layer for forming the rewiring formation layer is irradiated with actinic rays through a mask pattern, and a development step in which the non-exposed portion not irradiated with actinic rays is removed with a developer. An alkaline aqueous solution is preferred as the developer. The dose and duration of actinic rays can be appropriately set depending on the photosensitive resin composition layer. Examples of exposure methods include a contact exposure method in which a mask pattern is brought into close contact with the photosensitive resin composition layer and exposed, and a non-contact exposure method in which a mask pattern is not brought into close contact with the photosensitive resin composition layer and exposed using parallel rays. The actinic rays are the same as those used in step (II) of the first embodiment. The developer is the same as that used in step (III) of the first embodiment. The exposure and development method is the same as that used in steps (II) and (III) of the first embodiment.

[0321] The shape of the via hole is not particularly limited, but is preferably circular or approximately circular. The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less, and is preferably 0.1 μm or more, preferably 0.5 μm or more, and more preferably 1.0 μm or more. Here, the top diameter of the via hole refers to the diameter of the opening of the via hole on the surface of the rewiring formation layer.

[0322] <Process (F)> Step (F) is a step of forming a redistribution layer as a conductor layer on the redistribution formation layer. The method of forming the redistribution layer on the redistribution formation layer may be the same as the method of forming a conductor layer on an insulating layer in the first embodiment. Steps (E) and (F) may be repeated to alternately stack (build up) the redistribution layers and the redistribution formation layers.

[0323] <Process (G)> Step (G) is a step of forming a solder resist layer on the rewiring layer. Any insulating material can be used as the material for the solder resist layer. Among these, from the viewpoint of ease of manufacturing the semiconductor package substrate, a photosensitive resin or a thermosetting resin is preferred. The photosensitive resin composition of the present invention may also be used.

[0324] In step (G), bumping processing may be performed to form bumps, if necessary. The bumping processing can be performed by a method such as solder balls or solder plating. In addition, the formation of via holes in the bumping processing can be performed in the same manner as in step (E).

[0325] The method for manufacturing a semiconductor package substrate according to the second embodiment may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing a plurality of semiconductor package substrates into individual semiconductor package substrates. The method for dicing the semiconductor package substrates into individual semiconductor package substrates is not particularly limited.

[0326] [Semiconductor Devices] The semiconductor device of the present invention includes the semiconductor package substrate of the present invention described above. Examples of semiconductor devices on which the semiconductor package substrate described above is mounted include various semiconductor devices used in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0327] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0328] <Synthesis Example 1: Synthesis of polyimide polymer (A1)> 42.3 g of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA) was placed in a 2 L separable flask, followed by 488 g of γ-butyrolactone and stirring at room temperature. 24.4 g of 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid (MBAA) was added, and the flask was heated in an oil bath until the internal temperature reached 55 °C. Polymerization continued for 20 hours to obtain polyamic acid. Next, 138.7 g of toluene and 2.0 g of benzoic acid were added, and the mixture was heated until the internal temperature reached 150 °C. Dehydration and imidization were carried out for 5 hours via azeotropic distillation of toluene and water. The resulting solution was crystallized in 5 L of purified water, and the resulting solid was filtered and dried under reduced pressure at 80 °C for 40 hours to obtain 67 g of polyimide polymer.

[0329] Next, this polyimide polymer was again dissolved in γ-butyrolactone to a concentration of 25% by mass, and 11.0 g of 4-methoxyphenol (1% by mass solution in γ-butyrolactone), 60.0 g of glycidyl methacrylate (GMA), and 0.6 g of 2-ethyl-4-methylimidazole (2E4MZ) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyimide polymer (A1).

[0330] The molecular weight of the polyimide polymer (A1) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 26,000. The structural formula of the polyimide polymer (A1) is shown in the following formula (A-2-1). The modification rate u1 is expressed as follows: 1 The relative integral value per 1H of the corresponding peak in H-NMR measurement was confirmed to be 35.8%. a1 and R a2 Of these, 35.8% are groups represented by the following formula (X-4). [ka] (In formula (A-2-1), M is an integer of 5 to 200. R a1 and R a2 are each independently a hydrogen atom or a group represented by the following formula (X-4): [ka]

[0331] <Synthesis Example 2: Synthesis of Polyimide Polymer (A2)> 44.2 g of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA) was placed in a 2 L separable flask, followed by 506 g of γ-butyrolactone and stirring at room temperature. 24.4 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP) was then added, and the flask was heated in an oil bath to an internal temperature of 55 °C. Polymerization was carried out for 20 hours to obtain polyamic acid. Next, 143.7 g of toluene and 2.1 g of benzoic acid were added, and the mixture was heated to an internal temperature of 150 °C. Dehydration and imidization were carried out for 5 hours via azeotropic distillation of toluene and water. The resulting solution was crystallized in 5 L of purified water, and the resulting solid was filtered and dried under reduced pressure at 80 °C for 40 hours to obtain 64 g of polyimide polymer.

[0332] Next, this polyimide polymer was again dissolved in γ-butyrolactone to a concentration of 25% by mass, and 6.7 g of 4-methoxyphenol (1% by mass solution in γ-butyrolactone), 31.2 g of glycidyl methacrylate (GMA), and 0.4 g of 2-ethyl-4-methylimidazole (2E4MZ) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyimide polymer (A2).

[0333] The molecular weight of the polyimide polymer (A2) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 18,000. The structural formula of the polyimide polymer (A2) is shown in the following formula (A-2-2). The modification rate u1 is expressed as follows: 1 The relative integral value per 1H of the corresponding peak in H-NMR measurement was confirmed to be 43.7%. a1 and R a2 Of these, 43.7% are groups represented by the following formula (X-4). [ka] (In formula (A-2-2), M is an integer of 5 to 200. R a1 and R a2 are each independently a hydrogen atom or a group represented by the following formula (X-4): [ka]

[0334] <Synthesis Example 3: Synthesis of polyimide polymer (A3)> 42.9 g of 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) (TAHQ) was placed in a 2 L separable flask, followed by 524 g of γ-butyrolactone. The mixture was stirred at room temperature, and 28.5 g of 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid (MBAA) was added. The flask was heated in an oil bath to an internal temperature of 55°C and polymerized for 20 hours to obtain polyamic acid. Next, 148.8 g of toluene and 2.1 g of benzoic acid were added, and the mixture was heated to an internal temperature of 150°C. Dehydration and imidization were carried out for 5 hours via azeotropic distillation of toluene and water. The resulting solution was crystallized in 5 L of purified water, filtered, and dried under reduced pressure at 80°C for 40 hours to obtain 70 g of polyimide polymer.

[0335] Next, this polyimide polymer was again dissolved in γ-butyrolactone to a concentration of 25% by mass, and 7.4 g of 4-methoxyphenol (1% by mass solution in γ-butyrolactone), 35.1 g of glycidyl methacrylate (GMA), and 0.4 g of 2-ethyl-4-methylimidazole (2E4MZ) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyimide polymer (A3).

[0336] The molecular weight of the polyimide polymer (A3) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 24,000. The structural formula of the polyimide polymer (A3) is shown in the following formula (A-2-3). The modification rate u1 is expressed as follows: 1 The relative integral value per 1H of the corresponding peak in H-NMR measurement was confirmed to be 33.1%. a1 and R a2 Of these, 33.1% are groups represented by the following formula (X-4). [ka] (In formula (A-2-3), M is an integer of 5 to 200. R a1 and R a2are each independently a hydrogen atom or a group represented by the following formula (X-4): [ka]

[0337] <Synthesis Example 4: Synthesis of polyimide polymer (A4)> 41.4 g of 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) (TAHQ) was placed in a 2 L separable flask, followed by 505 g of γ-butyrolactone. The mixture was stirred at room temperature, and 27.4 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP) was added. The flask was heated in an oil bath to an internal temperature of 55 °C and polymerized for 20 hours to obtain polyamic acid. Next, 143.4 g of toluene and 2.1 g of benzoic acid were added, and the mixture was heated to an internal temperature of 150 °C. Dehydration and imidization were carried out for 5 hours via azeotropic distillation of toluene and water. The resulting solution was crystallized in 5 L of purified water, filtered, and dried under reduced pressure at 80 °C for 40 hours to obtain 66 g of polyimide polymer.

[0338] Next, this polyimide polymer was again dissolved in γ-butyrolactone to a concentration of 25% by mass, and 6.9 g of 4-methoxyphenol (1% by mass solution in γ-butyrolactone), 33.7 g of glycidyl methacrylate (GMA), and 0.4 g of 2-ethyl-4-methylimidazole (2E4MZ) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyimide polymer (A4).

[0339] The molecular weight of the polyimide polymer (A4) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 19,000. The structural formula of the polyimide polymer (A4) is shown in the following formula (A-2-4). The modification rate u1 is expressed as follows: 1 The relative integral value per 1H of the corresponding peak in H-NMR measurement was confirmed to be 46.0%. a1 and Ra2 Of these, 46.0% are groups represented by the following formula (X-4). [ka] (In formula (A-2-4), M is an integer of 5 to 200. R a1 and R a2 are each independently a hydrogen atom or a group represented by the following formula (X-4): [ka]

[0340] <Synthesis Example 5: Synthesis of polyimide polymer (A5)> 42.2 g of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA) was placed in a 2 L separable flask, followed by 516 g of γ-butyrolactone and stirring at room temperature. 26.2 g of 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid (MBAA) was then added, and the separable flask was heated in an oil bath to an internal temperature of 55 °C. Polymerization was carried out for 15 hours to obtain polyamic acid. 2.0 g of maleic anhydride was then added and terminal maleimidation was carried out at 55 °C for 5 hours. Next, 146.6 g of toluene and 2.1 g of benzoic acid were added, and the mixture was heated to an internal temperature of 150 °C. Dehydration and imidization were carried out by azeotropic distillation of toluene and water for 5 hours. The reaction solution was crystallized in 5 L of purified water, and the resulting solid was filtered and dried under reduced pressure at 80 °C for 40 hours to obtain 68 g of polyimide polymer.

[0341] Next, this polyimide polymer was again dissolved in γ-butyrolactone to a concentration of 25% by mass, and 7.7 g of 4-methoxyphenol (1% by mass solution in γ-butyrolactone), 42.3 g of glycidyl methacrylate (GMA), and 0.5 g of 2-ethyl-4-methylimidazole (2E4MZ) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyimide polymer (A5).

[0342] The molecular weight of the polyimide polymer (A5) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 26,000. The structural formula of the polyimide polymer (A5) is shown in the following formula (A-6-1). The modification rate u1 is expressed as follows: 1 The relative integral value per 1H of the corresponding peak in H-NMR measurement was confirmed to be 33.7%. a1 and R a2 Of these, 33.7% are groups represented by the following formula (X-4). [ka] (In formula (A-6-1), M is an integer of 5 to 200. R a1 and R a2 are each independently a hydrogen atom or a group represented by the following formula (X-4): [ka]

[0343] <Synthesis Example 6: Synthesis of polyimide polymer (A6)> 41.8 g of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA) was placed in a 2 L separable flask, followed by 493.4 g of γ-butyrolactone and stirring at room temperature. 23.4 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP) was then added, and the separable flask was heated in an oil bath to an internal temperature of 55 °C. Polymerization was carried out for 15 hours to obtain polyamic acid. 2.0 g of maleic anhydride was then added and terminal maleimidation was carried out at 55 °C for 5 hours. Next, 140.2 g of toluene and 2.0 g of benzoic acid were added, and the mixture was heated to an internal temperature of 150 °C. Dehydration and imidization were carried out by azeotropic distillation of toluene and water for 5 hours. The reaction solution was crystallized in 5 L of purified water, and the resulting solid was filtered and dried under reduced pressure at 80 °C for 40 hours to obtain 64 g of polyimide polymer.

[0344] Next, this polyimide polymer was again dissolved in γ-butyrolactone to a concentration of 25% by mass, and 6.6 g of 4-methoxyphenol (1% by mass solution in γ-butyrolactone), 30.8 g of glycidyl methacrylate (GMA), and 0.4 g of 2-ethyl-4-methylimidazole (2E4MZ) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyimide polymer (A6).

[0345] The molecular weight of the polyimide polymer (A6) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 22,000. The structural formula of the polyimide polymer (A6) is shown in the following formula (A-6-2). The modification rate u1 is expressed as follows: 1 The relative integral value per 1H of the corresponding peak in H-NMR measurement was confirmed to be 42.2%. a1 and R a2 Of these, 42.2% are groups represented by the following formula (X-4). [ka] (In formula (A-6-2), M is an integer of 5 to 200. R a1 and R a2 are each independently a hydrogen atom or a group represented by the following formula (X-4): [ka]

[0346] <Synthesis Example 7: Synthesis of polyimide polymer (A7)> 40.4 g of 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) (TAHQ) was placed in a 2 L separable flask, followed by 514.0 g of γ-butyrolactone. The mixture was stirred at room temperature, and 26.7 g of 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid (MBAA) was added. The flask was heated in an oil bath to an internal temperature of 55 °C and polymerized for 15 hours to obtain polyamic acid. 3.0 g of maleic anhydride was then added and terminal maleimidation was carried out at 55 °C for 5 hours. Next, 146.0 g of toluene and 2.1 g of benzoic acid were added, and the mixture was heated to an internal temperature of 150 °C. Dehydration and imidization were carried out by azeotropic distillation of toluene and water for 5 hours. The reaction solution was crystallized in 5 L of purified water, and the resulting solid was filtered and dried under reduced pressure at 80 °C for 40 hours to obtain 67 g of polyimide polymer.

[0347] Next, this polyimide polymer was again dissolved in γ-butyrolactone to a concentration of 25% by mass, and 7.0 g of 4-methoxyphenol (1% by mass solution in γ-butyrolactone), 33.6 g of glycidyl acrylate (GMA), and 0.4 g of 2-ethyl-4-methylimidazole (2E4MZ) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyimide polymer (A7).

[0348] The molecular weight of the polyimide polymer (A7) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 25,000. The structural formula of the polyimide polymer (A7) is shown in the following formula (A-6-3). The modification rate u1 is expressed as follows: 1 The relative integral value per 1H of the corresponding peak in H-NMR measurement was confirmed to be 29.9%. a1 and R a2 Of these, 29.9% are groups represented by the following formula (X-4). [ka] (In formula (A-6-3), M is an integer of 5 to 200. R a1and R a2 are each independently a hydrogen atom or a group represented by the following formula (X-4): [ka]

[0349] <Synthesis Example 8: Synthesis of polyimide polymer (A8)> 39.6 g of 1,4-phenylenebis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylate) (TAHQ) was placed in a 2 L separable flask, followed by 498.7 g of γ-butyrolactone. The mixture was stirred at room temperature, and 26.2 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP) was added. The flask was heated in an oil bath to an internal temperature of 55 °C and polymerized for 15 hours to obtain polyamic acid. 2.2 g of maleic anhydride was then added and terminal maleimidation was carried out at 55 °C for 5 hours. Next, 141.7 g of toluene and 2.0 g of benzoic acid were added, and the mixture was heated to an internal temperature of 150 °C. Dehydration and imidization were carried out by azeotropic distillation of toluene and water for 5 hours. The reaction solution was crystallized in 5 L of purified water, and the resulting solid was filtered and dried under reduced pressure at 80 °C for 40 hours to obtain 61 g of polyimide polymer.

[0350] Next, this polyimide polymer was again dissolved in γ-butyrolactone to a concentration of 25% by mass, and 6.5 g of 4-methoxyphenol (1% by mass solution in γ-butyrolactone), 31.7 g of glycidyl methacrylate (GMA), and 0.4 g of 2-ethyl-4-methylimidazole (2E4MZ) were added, and the mixture was heated to an internal temperature of 80°C and stirred for 15 hours to carry out an acrylic modification reaction, thereby obtaining polyimide polymer (A8).

[0351] The molecular weight of the polyimide polymer (A8) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 19,000. The structural formula of the polyimide polymer (A8) is shown in the following formula (A-6-4). The modification rate u1 is 1The relative integral value per 1H of the corresponding peak in H-NMR measurement was confirmed to be 44.0%. a1 and R a2 Of these, 44.0% are groups represented by the following formula (X-4). [ka] (In formula (A-6-4), M is an integer of 5 to 200. R a1 and R a2 are each independently a hydrogen atom or a group represented by the following formula (X-4): [ka]

[0352] <Comparative Synthesis Example 1: Synthesis of Polyimide Polymer (A'9)> 32.8 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was placed in a 2 L separable flask, followed by 494 g of γ-butyrolactone and stirring at room temperature. 34.6 g of 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid (MBAA) was then added, and the flask was heated in an oil bath to an internal temperature of 55 °C. Polymerization was carried out for 20 hours to obtain polyamic acid. Next, 140.3 g of toluene and 2.0 g of benzoic acid were added, and the mixture was heated to an internal temperature of 150 °C. Dehydration and imidization were carried out for 5 hours via azeotropic distillation of toluene and water. The resulting solution was crystallized in 5 L of purified water, and the resulting solid was filtered and dried under reduced pressure at 80 °C for 40 hours to obtain 65 g of polyimide polymer.

[0353] Next, this polyimide polymer was again dissolved in γ-butyrolactone to a concentration of 25% by mass, and 7.4 g of 4-methoxyphenol (1% by mass solution in γ-butyrolactone), 40.4 g of glycidyl methacrylate (GMA), and 0.4 g of 2-ethyl-4-methylimidazole (2E4MZ) were added.The mixture was heated to an internal temperature of 80°C and stirred for 15 hours to perform an acrylic modification reaction, yielding polyimide polymer (A'9).

[0354] The molecular weight of the polyimide polymer (A'9) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 35,000. The structural formula of the polyimide polymer (A'9) is shown in the following formula (A'-2-5). The modification rate u1 is 1 The relative integral value per 1H of the corresponding peak in H-NMR measurement was 32.8%. a1 and R a2 Of these, 32.8% are groups represented by the following formula (X-4). [ka] (In formula (A'-2-5), M is an integer of 5 to 200. R a1 and R a2 are each independently a hydrogen atom or a group represented by the following formula (X-4): [ka]

[0355] <Comparative Synthesis Example 2: Synthesis of Polyimide Polymer (A'10)> 34.4 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was placed in a 2 L separable flask, followed by 493 g of γ-butyrolactone and stirring at room temperature. 32.8 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP) was then added, and the flask was heated in an oil bath to an internal temperature of 55 °C. Polymerization was carried out for 20 hours to obtain polyamic acid. Next, 140.0 g of toluene and 2.0 g of benzoic acid were added, and the mixture was heated to an internal temperature of 150 °C. Dehydration and imidization were carried out for 5 hours via azeotropic distillation of toluene and water. The resulting solution was crystallized in 5 L of purified water, and the resulting solid was filtered and dried under reduced pressure at 80 °C for 40 hours to obtain 67 g of polyimide polymer.

[0356] Next, this polyimide polymer was again dissolved in γ-butyrolactone to a concentration of 25% by mass, and 7.7 g of 4-methoxyphenol (1% by mass solution in γ-butyrolactone), 43.4 g of glycidyl methacrylate (GMA), and 0.4 g of 2-ethyl-4-methylimidazole (2E4MZ) were added.The mixture was heated to an internal temperature of 80°C and stirred for 15 hours to perform an acrylic modification reaction, yielding polyimide polymer (A'10).

[0357] The molecular weight of the polyimide polymer (A'10) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be 29,000 in weight average molecular weight (Mw). The structural formula of the polyimide polymer (A'10) is shown in the following formula (A'-2-6). The modification rate u1 is 1 The relative integral value per 1H of the corresponding peak in H-NMR measurement was confirmed to be 40.8%. a1 and R a2 Of these, 40.8% are groups represented by the following formula (X-4). [ka] (In formula (A'-2-6), M is an integer of 5 to 200. R a1 and R a2 are each independently a hydrogen atom or a group represented by the following formula (X-4): [ka]

[0358] <Comparative Synthesis Example 3: Synthesis of Polyimide Polymer (A'11)> 40.2 g of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) was placed in a 2 L separable flask, followed by 501 g of γ-butyrolactone and stirring at room temperature. 28.1 g of 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid (MBAA) was then added, and the flask was heated in an oil bath to an internal temperature of 55°C. Polymerization was carried out for 20 hours to obtain polyamic acid. Next, 142.3 g of toluene and 2.0 g of benzoic acid were added, and the mixture was heated to an internal temperature of 150°C. Dehydration and imidization were carried out for 5 hours via azeotropic distillation of toluene and water. The resulting solution was crystallized in 5 L of purified water, and the resulting solid was filtered and dried under reduced pressure at 80°C for 40 hours to obtain 64 g of polyimide polymer.

[0359] Next, this polyimide polymer was again dissolved in γ-butyrolactone to a concentration of 25% by mass, and 6.8 g of 4-methoxyphenol (1% by mass solution in γ-butyrolactone), 32.6 g of glycidyl methacrylate (GMA), and 0.4 g of 2-ethyl-4-methylimidazole (2E4MZ) were added.The mixture was heated to an internal temperature of 80°C and stirred for 15 hours to perform an acrylic modification reaction, yielding polyimide polymer (A'11).

[0360] The molecular weight of the polyimide polymer (A'11) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be a weight average molecular weight (Mw) of 33,000. The structural formula of the polyimide polymer (A'11) is shown in the following formula (A'-2-7). The modification rate u1 is 1 The relative integral value per 1H of the corresponding peak in H-NMR measurement was confirmed to be 28.9%. a1 and R a2 Of these, 28.9% are groups represented by the following formula (X-4). [ka] (In formula (A'-2-7), M is an integer of 5 to 200. R a1 and R a2are each independently a hydrogen atom or a group represented by the following formula (X-4): [ka]

[0361] Comparative Synthesis Example 4: Synthesis of Polyimide Polymer (A'12) 34.3 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) was placed in a 2 L separable flask, followed by 493 g of γ-butyrolactone and stirring at room temperature. 33.0 g of 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid (MBAA) was then added, and the separable flask was heated in an oil bath until the internal temperature reached 55°C. Polymerization continued for 20 hours to obtain polyamic acid. Next, 140.1 g of toluene and 2.0 g of benzoic acid were added, and the mixture was heated until the internal temperature reached 150°C. Dehydration and imidization were carried out for 5 hours via azeotropic distillation of toluene and water. The resulting solution was crystallized in 5 L of purified water, and the resulting solid was filtered and dried under reduced pressure at 80°C for 40 hours to obtain 67 g of polyimide polymer.

[0362] Next, this polyimide polymer was again dissolved in γ-butyrolactone to a concentration of 25% by mass, and 7.5 g of 4-methoxyphenol (1% by mass solution in γ-butyrolactone), 40.6 g of glycidyl methacrylate (GMA), and 0.4 g of 2-ethyl-4-methylimidazole (2E4MZ) were added.The mixture was heated to an internal temperature of 80°C and stirred for 15 hours to perform an acrylic modification reaction, yielding polyimide polymer (A'12).

[0363] The molecular weight of the polyimide polymer (A'12) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 19,000. The structural formula of the polyimide polymer (A'12) is shown in the following formula (A'-2-8). The modification rate u1 is 1 The relative integral value per 1H of the corresponding peak in H-NMR measurement was 31.6%. a1 and R a2Of these, 31.6% are groups represented by the following formula (X-4). [ka] (In formula (A'-2-8), M is an integer of 5 to 200. R a1 and R a2 are each independently a hydrogen atom or a group represented by the following formula (X-4): [ka]

[0364] The measurement results of the obtained polyimide polymer are shown in Table 1. [Table 1]

[0365] <Examples 1 to 12 and Comparative Examples 1 to 4: Preparation of Photosensitive Resin Compositions> The polyimide polymers (A1) to (A8) synthesized in Synthesis Examples 1 to 8, the polyimide polymers (A'9) to (A'12) synthesized in Comparative Synthesis Examples 1 to 4, (B) a photopolymerization initiator, (C) a crosslinking agent, (D) an adhesion aid, (E) a sensitizer, and (F) a surfactant were mixed as shown in Table 2 below and stirred using a high-speed rotating mixer to prepare a photosensitive resin composition. Furthermore, the photosensitive resin composition was dissolved in cyclohexanone as a solvent (G) to prepare a varnish-like photosensitive resin composition. [Table 2]

[0366] The abbreviations in the table are as follows: (B) Photopolymerization initiator Irgacure OXE02: An oxime ester photoinitiator represented by the following structural formula (BASF's "Irgacure OXE02") [ka]

[0367] (C) Crosslinker TMPT: A compound represented by the following structural formula ("TMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) [ka] BANI-X: A compound represented by the following structural formula [ka]

[0368] (D) Adhesion aid KBM-403: A compound represented by the following structural formula [ka]

[0369] (E) Sensitizer UVS-581: A compound represented by the following structural formula [ka]

[0370] (F) Surfactant KP-341: Polyether surfactant (Shin-Etsu Chemical Co., Ltd. "KP-341")

[0371] <Preparation of photosensitive film> A PET film ("Lumirror T6AM" manufactured by Toray Industries, Inc., thickness 38 μm) was prepared as a support. The photosensitive resin composition prepared in each example and comparative example was uniformly applied to the PET film using a die coater so that the film thickness of the photosensitive resin composition layer after drying would be 10 μm, and the film was dried at 80 to 120°C for 6 minutes to form a photosensitive resin composition layer on the PET. Next, a protective film (biaxially oriented polypropylene film, "MA-411" manufactured by Oji F-Tex Co., Ltd.) was placed on the surface of the photosensitive resin composition layer and laminated at 80°C to produce a photosensitive film with a three-layer structure of support / photosensitive resin composition layer / protective film.

[0372] <Evaluation of development time and limiting resolution> A 5 μm thick copper plating was laminated on a silicon wafer and roughened with a 1% hydrochloric acid solution for 10 seconds to prepare a substrate. The protective film on the photosensitive film prepared by the above method was removed, and the photosensitive resin composition layer of the photosensitive film was placed on the roughened substrate so that it was in contact with the surface of the copper layer. After lamination, the support was removed, and the substrate was heated on a hot plate at 120°C for 1 minute to produce a photosensitive resin composition layer. This is called a laminate.

[0373] The laminate was irradiated with ultraviolet light (wavelength 365 nm, intensity 40 mW / cm 2 The exposure was performed at a dose of 50 mJ / cm. 2 to 1000mJ / cm 2 The optimum value was set in the range of 1. For the exposure pattern, a quartz glass mask was used to draw round holes (vias) with opening diameters of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm.

[0374] Next, a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) was sprayed as a developer onto the entire surface of the exposed laminated photosensitive resin composition layer at a spray pressure of 0.1 MPa for an optimal time between 30 and 600 seconds to perform development, followed by rinsing with pure water at a spray pressure of 0.1 MPa for 30 seconds. The photosensitive resin composition layer was then cured by heat treatment at 160°C for 120 minutes. The development time is shown in Table 2. The development time was evaluated according to the following criteria. ○: Development time is 240 seconds or less ×: Development time is longer than 240 seconds

[0375] The diameters of the bottoms of vias with openings of 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm in the exposure pattern were observed and measured using a scanning electron microscope (SEM) at a magnification of 1000x. The minimum size that can be opened is defined as the limiting resolution, and it was evaluated according to the following criteria. ○: The minimum opening size is 10 μm or less △: The minimum opening size is greater than 10 μm and less than 20 μm ×: The minimum size that can be opened is greater than 20 μm

[0376] <Preparation of film for measuring physical properties> The photosensitive resin compositions prepared in the Examples and Comparative Examples were coated onto a release-treated PET film using a blade to a film thickness of 140 μm. The solution on the PET was heated at 80°C for 15 minutes using a heater to form a photosensitive film having a photosensitive resin composition layer. The photosensitive resin composition layer was peeled from the PET film, and the photosensitive resin composition layer was attached to a metal frame using heat-resistant tape. The layer was then heated at 1000 mJ / cm. 2 The film was then heated at 160°C for 2 hours to prepare a film for measuring physical properties.

[0377] <Measurement of coefficient of linear thermal expansion (CTE)> The film for measuring physical properties was cut into a width of 5 mm and a length of 15 mm to obtain a test specimen. This test specimen was subjected to thermomechanical analysis by the tensile load method using a thermomechanical analyzer (Rigaku Corporation, "Thermo Plus TMA8310"). Specifically, the test specimen was mounted in the thermomechanical analyzer and subjected to two consecutive measurements under the conditions of a load of 1 g and a heating rate of 5°C / min (the first measurement was performed at 200°C, and the second measurement was performed at 260°C). In the second measurement, the coefficient of linear thermal expansion (CTE) in the planar direction over a temperature range of 25°C to 150°C was calculated and evaluated according to the following criteria. ○: Coefficient of linear thermal expansion CTE is 65 ppm / ℃ or less ×: Coefficient of linear thermal expansion CTE is greater than 65 ppm / °C

[0378] <Measurement of glass transition temperature (Tg)> The film for measuring physical properties was cut into test pieces approximately 5 mm wide and 15 mm long, and thermomechanical analysis was performed using a thermomechanical analyzer (Rigaku Corporation, "Thermo Plus TMA8310") by the tensile load method. Specifically, the test pieces were mounted in the thermomechanical analyzer and measured twice consecutively under the conditions of a load of 1 g and a heating rate of 5°C / min (the first time the temperature was raised to 200°C, and the second time the temperature was raised to 260°C). The glass transition temperature Tg (°C) was calculated from the second measurement and evaluated according to the following criteria. ○: Glass transition temperature Tg is 175°C or higher ×: Glass transition temperature Tg is less than 175°C

[0379] <Measurement of elongation at break and elastic modulus> The film for measuring physical properties was cut into a No. 1 dumbbell shape to obtain a test piece. The test piece was subjected to tensile strength measurement using an Orientec tensile testing machine "RTC-1250A" to determine the elongation at break and modulus of elasticity at 25°C. The measurement was carried out in accordance with JIS K7127. Three measurements were carried out and the average value was used as the measurement result. The elongation at break was evaluated according to the following criteria (unit of elongation at break: %, unit of modulus of elasticity: GPa). ○: Elongation at break is 25% or more ×: Elongation at break is less than 25%

[0380] <Measurement of dielectric properties (dielectric constant Dk, dielectric loss tangent Df)>

[0381] A test piece measuring 2 mm in width and 80 mm in length was cut from the film for measuring physical properties. The dielectric constant Dk and dielectric loss tangent Df of the cut test piece were measured by the cavity resonance perturbation method using an Agilent Technologies HP8362B measuring device at a measurement frequency of 2.8 GHz and a measurement temperature of 23°C.

[0382] Examples 1 to 12, which contained component (A) having the specified structure of the present invention, were capable of curing at a low temperature of 160°C, and when developed with an alkaline aqueous solution at room temperature, development was possible in a short time. Furthermore, the resulting cured products exhibited a low linear expansion coefficient, a high glass transition temperature, and a high elongation at break. On the other hand, Comparative Examples 1 to 4 required a long development time due to poor solubility in alkaline aqueous solution, resulting in poor productivity and unsatisfactory elongation at break, glass transition temperature, and linear thermal expansion coefficient of the cured products. It was also confirmed that, even when the sensitizer (E) was not included, increasing the exposure dose yielded similar results to those of the above examples, although to varying degrees.

Claims

1. (A) a polyimide polymer having a structure derived from a tetracarboxylic dianhydride having an ether structure or an ester structure and a structure derived from a diamine having a hydroxy structure, in which a part or all of the hydroxy structures are modified with a structure derived from an epoxy compound having an ethylenically unsaturated bond; A photosensitive resin composition comprising:

2. 2. The photosensitive resin composition according to claim 1, which is a negative photosensitive resin composition.

3. The photosensitive resin composition according to claim 1 , wherein the structure derived from the tetracarboxylic dianhydride in the component (A) has an ether structure.

4. The photosensitive resin composition according to claim 1 , wherein the structure derived from the tetracarboxylic dianhydride in the component (A) has an ester structure.

5. 2. The photosensitive resin composition according to claim 1, wherein the epoxy compound having an ethylenically unsaturated bond in component (A) is glycidyl (meth)acrylate.

6. 2. The photosensitive resin composition according to claim 1, wherein the hydroxy structure in the component (A) is a hydroxycarbonyl group or a phenolic hydroxy group.

7. 2. The photosensitive resin composition according to claim 1, wherein the modification of the hydroxy structure in the component (A) is etherification or esterification.

8. In component (A), the sum of the number of modified hydroxy structures and the number of unmodified hydroxy structures is T １ , the number of modified hydroxy structures is S １ When the modification rate is u １ 2. The photosensitive resin composition according to claim 1, wherein (%) is 10 to 90%. [Equation 1]

9. 2. The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-1): 【Chemical 1】 (In formula (A-1), M represents an integer of 1 or more. A １ A each independently represents a tetravalent organic group having an ether structure or an ester structure. ２ each independently represents a divalent organic group having one or more groups selected from a hydroxy group, a hydroxycarbonyl group, an oxycarbonyl group having an ethylenically unsaturated bond, and an alkoxy group having an ethylenically unsaturated bond, and A in the M repeating units ２ At least one of the groups has one or more groups selected from an oxycarbonyl group having an ethylenically unsaturated bond and an alkoxy group having an ethylenically unsaturated bond.

10. In formula (A-1), A １ The photosensitive resin composition according to claim 9, wherein is a tetravalent organic group represented by the following formula (X-3): 【Chemistry 2】 (In formula (X-3), nc represents an integer of 0 or more. １ , Ring Ar ２ and ring Ar ３ each independently represents an aromatic carbocyclic ring having 6 to 10 carbon atoms. １ and L ２ each independently represents a single bond, an oxygen atom, an ester bond, or an alkylene group having 1 to 5 carbon atoms which may have a halogen atom as a substituent; L １ and n c L ２ At least one of the groups is an oxygen atom or an ester bond. * represents a bond.

11. 2. The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-2): 【Chemistry 3】 (In formula (A-2), M represents an integer of 1 or more. q1 and q2 each independently represent an integer of 1 to 4. A １ Each X independently represents a tetravalent organic group having an ether structure or an ester structure. Each X independently represents a single bond, an oxygen atom, a sulfur atom, an ester bond, an alkylene group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an arylene group having 4 to 20 carbon atoms, or a divalent group consisting of a combination thereof. Y １ and Y ２ each independently represents a hydroxy group, a hydroxycarbonyl group, a group represented by the following formula (X-1), or a group represented by the following formula (X-2), and Y in the M repeating units １ and Y ２ At least one of the above is a group represented by the following formula (X-1) or a group represented by the following formula (X-2): 【Chemistry 4】 (In formula (X-1), R １４ , R １５ and R １６ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. ａ１ represents an oxygen atom or an ester bond. １ represents an integer of 0 to 10. * represents a bond. 【Chemistry 5】 In formula (X-2), ring Z represents an aliphatic hydrocarbon ring having 3 to 20 carbon atoms, which may have a substituent. ２４ , R ２５ and R ２６ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. ａ２ represents an oxygen atom or an ester bond. ２ represents an integer of 0 to 10. * represents a bond.

12. 12. The photosensitive resin composition according to claim 11, wherein in formula (A-2), X is an alkylene group having 1 to 5 carbon atoms.

13. In formula (A-2), Y １ and Y ２ are each independently a hydroxy group, a hydroxycarbonyl group, or a group represented by the above formula (X-1), In formula (X-1), R １４ is a hydrogen atom or a methyl group, and R １５ is a hydrogen atom, and R １６ is a hydrogen atom, and p １ The photosensitive resin composition according to claim 11, wherein

14. 2. The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-2-1): 【Chemistry 6】 (In formula (A-2-1), M represents an integer of 1 or more. R ａ１ and R ａ２ each independently represents a hydrogen atom or a group represented by the following formula (X-4), and R ａ１ and R ａ２ At least one of the above is a group represented by the following formula (X-4): 【Chemistry 7】

15. 2. The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-2-2): 【Chemistry 8】 (In formula (A-2-2), M represents an integer of 1 or more. R ａ１ and R ａ２ each independently represents a hydrogen atom or a group represented by the following formula (X-4), and R ａ１ and R ａ２ At least one of the above is a group represented by the following formula (X-4): 【Chemistry 9】

16. 2. The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-2-3): 【Chemistry 10】 (In formula (A-2-3), M represents an integer of 1 or more. R ａ１ and R ａ２ each independently represents a hydrogen atom or a group represented by the following formula (X-4), and R ａ１ and R ａ２ At least one of the above is a group represented by the following formula (X-4): 【Chemistry 11】

17. 2. The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide polymer having a structural unit represented by the following formula (A-2-4): 【Chemistry 12】 (In formula (A-2-4), M represents an integer of 1 or more. R ａ１ and R ａ２ each independently represents a hydrogen atom or a group represented by the following formula (X-4), and R ａ１ and R ａ２ At least one of the above is a group represented by the following formula (X-4): 【Chemistry 13】

18. 2. The photosensitive resin composition according to claim 1, wherein at least one terminal of the main chain of the component (A) is a maleimide group.

19. 2. The photosensitive resin composition according to claim 1, wherein both ends of the main chain of the component (A) are maleimide groups.

20. 2. The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide polymer represented by the following formula (A-4): 【Chemistry 14】 (In formula (A-4), M represents an integer of 1 or more. １ A each independently represents a tetravalent organic group having an ether structure or an ester structure. ２ each independently represents a divalent organic group having one or more groups selected from a hydroxy group, a hydroxycarbonyl group, an oxycarbonyl group having an ethylenically unsaturated bond, and an alkoxy group having an ethylenically unsaturated bond, and A in the M+1 repeating units ２ At least one of the groups has one or more groups selected from an oxycarbonyl group having an ethylenically unsaturated bond and an alkoxy group having an ethylenically unsaturated bond.

21. The photosensitive resin composition according to claim 9, wherein m defined in the following formula (2) is 90 to 100, where M is the number of repetitions of the structural unit represented by formula (A-1) and, if any, N is the number of repetitions of the other structural units: [Equation 2]

22. 10. The photosensitive resin composition according to claim 9, wherein in formula (A-1), M is an integer of 5 to 200.

23. The photosensitive resin composition according to claim 1 , further comprising (B) a photopolymerization initiator.

24. The photosensitive resin composition according to claim 1 , further comprising (C) a crosslinking agent.

25. The photosensitive resin composition according to claim 1 , further comprising (D) an adhesion aid.

26. The photosensitive resin composition according to claim 1 , further comprising (E) a sensitizer.

27. The photosensitive resin composition according to claim 1 , further comprising (F) a surfactant.

28. A photosensitive film comprising a support and a photosensitive resin composition layer formed on the support, the photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 27.

29. A semiconductor package substrate comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of claims 1 to 27.

30. A semiconductor device comprising the semiconductor package substrate of claim 29.

31. A step of forming a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 27 on a circuit board; and a step of irradiating the photosensitive resin composition layer with actinic rays to perform development; A method for manufacturing a semiconductor package substrate, comprising:

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