JP2018162434A - Phenolic hydroxyl group-containing resin, photosensitive resin composition, semiconductor device, and electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phenolic hydroxyl group-containing resin and a photosensitive resin composition excellent in solubility in a developer, a semiconductor device including a cured product of the photosensitive resin composition, and an electronic apparatus including the semiconductor device.SOLUTION: The phenolic hydroxyl group-containing resin has a structure represented by formula (1a) [X is a C1-30 organic group; Y is H, an alkyl, a cycloalkyl, or an aryl; each R is independently OH, a halogen, a carboxyl, a C1-20 saturated/unsaturated alkyl, a C1-20 alkyl ether, a C3-20 saturated/unsaturated alicyclic group, or a C6-20 aromatic group and may be bonded via an ester, ether, amide or carbonyl bond group; and p is an integer of 0-3].SELECTED DRAWING: None

Description

  The present invention relates to a phenolic hydroxyl group-containing resin, a photosensitive resin composition, a semiconductor device, and an electronic apparatus.

  For semiconductor elements, resin films made of resin materials are used for applications such as protective films, interlayer insulating films, and planarization films.

  For example, Patent Document 1 proposes a photosensitive resin composition containing a polyamide resin, a photosensitive material, a phenol resin, and an adhesion assistant. Such a photosensitive resin composition is used as a protective film for protecting a semiconductor chip from external force, thermal shock, and the like by being applied to the surface of the semiconductor chip.

  Patent Document 2 proposes a positive photosensitive resin composition containing a novolac-type phenol resin, a quinonediazide group-containing compound, and a solvent. Since such a positive photosensitive resin composition can produce a cured product having excellent physical properties such as heat resistance, it contributes to the realization of a protective film with good heat resistance.

  On the other hand, in the manufacturing process of such a protective film, fine processing for exposing the terminals and the like is required. For example, after the resin film is formed, the resin film is processed by a process such as exposure and development. For this reason, the resin film is required to have good solubility in a developer.

JP 2013-174843 A JP 2012-107090 A

  However, the conventional photosensitive resin composition may not be sufficiently dissolved in the developer. In this case, the resin film cannot be sufficiently removed, and so-called development residue occurs.

  An object of the present invention is to provide a phenolic hydroxyl group-containing resin and a photosensitive resin composition excellent in solubility in a developer, a semiconductor device including a cured product of the photosensitive resin composition, and an electronic device including the semiconductor device. There is to do.

［式中、Ｘは、炭素数１〜３０の有機基であり、Ｙは、水素原子、アルキル基、シクロアルキル基またはアリール基であり、Ｒは、それぞれ独立して、水酸基、ハロゲン原子、カルボキシル基、炭素数１〜２０の飽和または不飽和のアルキル基、炭素数１〜２０のアルキルエーテル基、炭素数３〜２０の飽和または不飽和の脂環式基、および炭素数６〜２０の芳香族構造を有する有機基からなる群から選ばれる一価の置換基であって、前記置換基はエステル結合、エーテル結合、アミド結合、またはカルボニル結合を介して結合していてもよい。また、ｐは０〜３の整数である。］ Such an object is achieved by the present inventions (1) to (8) below.
(1) A phenolic hydroxyl group-containing resin having a structure represented by the following formula (1a).

[Wherein X is an organic group having 1 to 30 carbon atoms, Y is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R is independently a hydroxyl group, a halogen atom or a carboxyl group. Group, saturated or unsaturated alkyl group having 1 to 20 carbon atoms, alkyl ether group having 1 to 20 carbon atoms, saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, and fragrance having 6 to 20 carbon atoms It is a monovalent substituent selected from the group consisting of organic groups having a group structure, and the substituent may be bonded via an ester bond, an ether bond, an amide bond, or a carbonyl bond. Moreover, p is an integer of 0-3. ]

［式中、Ｘは、炭素数１〜３０の有機基であり、Ｙは、水素原子、アルキル基、シクロアルキル基またはアリール基であり、Ｒは、それぞれ独立して、水酸基、ハロゲン原子、カルボキシル基、炭素数１〜２０の飽和または不飽和のアルキル基、炭素数１〜２０のアルキルエーテル基、炭素数３〜２０の飽和または不飽和の脂環式基、および炭素数６〜２０の芳香族構造を有する有機基からなる群から選ばれる一価の置換基であって、前記置換基はエステル結合、エーテル結合、アミド結合、またはカルボニル結合を介して結合していてもよい。また、ｐは０〜３の整数である。］ (2) The phenolic hydroxyl group-containing resin according to the above (1), which has a structure represented by the following formula (1b).

[Wherein X is an organic group having 1 to 30 carbon atoms, Y is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R is independently a hydroxyl group, a halogen atom or a carboxyl group. Group, saturated or unsaturated alkyl group having 1 to 20 carbon atoms, alkyl ether group having 1 to 20 carbon atoms, saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, and fragrance having 6 to 20 carbon atoms It is a monovalent substituent selected from the group consisting of organic groups having a group structure, and the substituent may be bonded via an ester bond, an ether bond, an amide bond, or a carbonyl bond. Moreover, p is an integer of 0-3. ]

  (3) X is any one of an alkyl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an alkyloxyalkyl group having 4 to 12 carbon atoms. The phenolic hydroxyl group-containing resin according to the above (1) or (2).

  (4) The phenolic hydroxyl group-containing resin according to any one of (1) to (3), wherein X is any one of a hexyl group, a cyclohexyl group, a benzyl group, and a methoxyethyl group.

(5) the phenolic hydroxyl group-containing resin according to any one of (1) to (4) above;
A photosensitizer,
The photosensitive resin composition characterized by having.

(6) the phenolic hydroxyl group-containing resin according to any one of (1) to (4) above,
A crosslinking agent capable of crosslinking with the phenolic hydroxyl group-containing resin;
A photosensitizer,
The photosensitive resin composition characterized by having.

(7) a semiconductor substrate;
A coating layer provided on the surface of the semiconductor substrate and containing a cured product of the photosensitive resin composition according to the above (5) or (6);
A semiconductor device comprising:
(8) An electronic apparatus comprising the semiconductor device according to (7).

  According to the present invention, a phenolic hydroxyl group-containing resin and a photosensitive resin composition excellent in solubility in a developer can be obtained.

Moreover, according to this invention, the semiconductor device containing the hardened | cured material of the said photosensitive resin composition is obtained.
In addition, according to the present invention, an electronic apparatus including the semiconductor device can be obtained.

It is a longitudinal cross-sectional view which shows embodiment of the semiconductor device of this invention.

  Hereinafter, a phenolic hydroxyl group-containing resin, a photosensitive resin composition, a semiconductor device, and an electronic apparatus of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.

<Semiconductor device>
First, prior to the description of the phenolic hydroxyl group-containing resin and the photosensitive resin composition, an embodiment of the semiconductor device of the present invention to which these are applied will be described.

  FIG. 1 is a longitudinal sectional view showing an embodiment of a semiconductor device of the present invention. In the following description, the upper side in FIG. 1 is referred to as “upper” and the lower side is referred to as “lower”.

  A semiconductor device 10 shown in FIG. 1 is a QFP (Quad Flat Package) type semiconductor package containing a semiconductor chip 20, and a die pad that supports the semiconductor chip 20 via a semiconductor chip 20 (semiconductor substrate) and an adhesive layer 60. 30, a protective film 70 (covering layer) that protects the semiconductor chip 20, leads 40 electrically connected to the semiconductor chip 20, and a mold part 50 that seals the semiconductor chip 20. As described later in detail, such a semiconductor device 10 has high reliability due to the protective action of the protective film 70.

  The die pad 30 is made of a metal substrate and has a function as a support for supporting the semiconductor chip 20.

  The die pad 30 includes a metal substrate made of various metal materials such as Cu, Fe, Ni, and alloys thereof (for example, Cu-based alloys and iron / nickel-based alloys such as Fe-42Ni), and the metal substrates. The surface of which is plated with silver or Ni—Pd, and the surface of Ni—Pd is further provided with a gold plating layer provided to improve the stability of the Pd layer. It is done.

  Moreover, the planar view shape of the die pad 30 usually corresponds to the planar view shape of the semiconductor chip 20 and is, for example, a square such as a square or a rectangle.

A plurality of leads 40 are provided radially on the outer periphery of the die pad 30.
An end portion of the lead 40 opposite to the die pad 30 protrudes (exposes) from the mold portion 50.

  Further, the exposed portion of the lead 40 from the mold portion 50 may be subjected to surface treatment such as gold plating, tin plating, solder plating, or solder coating on the surface thereof.

  The lead 40 is made of a conductive material, and for example, the same material as that of the die pad 30 described above can be used.

  The semiconductor chip 20 is fixed (fixed) to the die pad 30 via the adhesive layer 60.

  The adhesive layer 60 has a function of connecting the die pad 30 and the semiconductor chip 20 and also has a function of transmitting (dissipating) heat generated when the semiconductor chip 20 is driven to the die pad 30 side.

  The adhesive layer 60 includes, for example, a metal powder such as silver powder, aluminum powder, and nickel powder, or ceramic powder such as silica powder, alumina powder, and titania powder as an filler, an epoxy resin, an acrylic compound, Those composed of a thermosetting resin such as polyimide resin are preferably used.

The semiconductor chip 20 has an electrode pad 21 on its upper surface, and the electrode pad 21 and the lead 40 are electrically connected by a conductive wire 22. Thereby, the semiconductor chip 20 and each lead 40 are electrically connected.
The conductive wire 22 can be composed of, for example, Au wire or Al wire.

  A protective film 70 is formed on the semiconductor chip 20 so that the electrode pads 21 are exposed.

  The protective film 70 has a function of protecting the semiconductor chip 20 when the mold part 50 is cured and contracted, a thermal shock in a solder reflow process for mounting the semiconductor device 10 on a substrate or the like, and a rapid heat of the mold part 50. It has a function of protecting against expansion stress.

  In the semiconductor device 10 according to the present embodiment, the protective film 70 is formed using the photosensitive resin composition according to the present embodiment. The constituent materials of the photosensitive resin composition will be described in detail later. To do.

  Furthermore, the die pad 30, each member provided on the upper surface side of the die pad 30, and the portion inside the lead 40 are sealed by the mold part 50. As a result, the outer end portion of the lead 40 protrudes from the mold portion 50.

  This mold part 50 can be comprised with various resin materials, such as an epoxy-type resin, for example.

<Method for Manufacturing Semiconductor Device>
Such a semiconductor device 10 can be manufactured as follows, for example.

  [1] First, a lead frame including a die pad 30 and a plurality of leads 40 is prepared.

  [2] Next, separately from this, the semiconductor chip 20 provided with the protective film 70 patterned so as to expose the electrode pads 21 is prepared.

  Such a protective film 70 can be formed on the semiconductor chip 20 as follows, for example.

  [2-1] First, the photosensitive resin composition of the present invention is prepared as a liquid material (varnish), and this liquid material is supplied using a coating method so as to cover almost the entire top surface of the semiconductor chip 20. .

Examples of the coating method include a spin coating method using a spinner, a spray coating method using a spray coater, a dipping method, a printing method, a roll coating method, and the like. Can be used in combination.
The coating amount is appropriately set according to the thickness of the protective film 70 to be formed.

  [2-2] Next, by drying the liquid material, a film containing the constituent material contained in the photosensitive resin composition is formed on the upper surface of the semiconductor chip 20.

  In addition, the drying temperature at the time of drying a liquid material becomes like this. Preferably it is about 40-150 degreeC, More preferably, it is set to about 80-130 degreeC.

  Moreover, it is preferable that the processing time at the time of drying is about 0.5 to 30 minutes, and it is more preferable that it is about 1 to 10 minutes.

  [2-3] Next, the film formed at a position corresponding to the electrode pad 21 is selectively exposed and exposed using a mask corresponding to the shape of the electrode pad 21, and then an alkaline aqueous solution or an organic solvent is used. Develop with developer. Thereby, the film is patterned into a shape in which the electrode pad 21 is exposed.

The light applied to the film formed using the photosensitive resin composition at the time of exposure / sensitivity is not particularly limited, and g-line (436 nm) and i-line (365 nm) are usually used, but i-line is particularly preferable. (365 nm) is preferably used. Thereby, the film can be surely patterned into a fine shape. Furthermore, when irradiating i line | wire at room temperature, energy amount is set to about 100-5000mJ / cm < ² >.

  Further, the aqueous alkali solution (alkaline developer) is not particularly limited. For example, in addition to organic alkali such as tetramethylammonium hydroxide, triethylamine, ethanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate Inorganic alkalis such as these can be used, and one or more of these can be used in combination. Especially, the tetramethylammonium hydroxide aqueous solution currently used by the semiconductor process is used suitably. The concentration of the tetramethylammonium hydroxide aqueous solution is set to about 0.05 to 10% by mass, preferably about 0.1 to 5% by mass. And it develops for 10 seconds-10 minutes at room temperature using this alkaline aqueous solution, and also by rinsing with a pure water, a clear positive pattern can be obtained.

  In some cases, alcohols may be added to the alkaline aqueous solution. Examples of usable alcohols include methanol, ethanol, 1-propanol, 2-propanol and the like.

  The organic solvent (organic developer) is not particularly limited, and may be a lactone such as γ-butyrolactone, acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone, or the like. Ketones, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol monoacetate, etc. A compound having an ester bond, monomethyl ether, monoethyl ether of the polyhydric alcohol or the compound having an ester bond , Derivatives of polyhydric alcohols such as monoalkyl ethers such as monopropyl ether and monobutyl ether or compounds having an ether bond such as monophenyl ether [in these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred]; cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxypropion Esters such as ethyl acid; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethyl benzene, die Aromatic organic solvents such as tilbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene and mesitylene, dimethyl sulfoxide (DMSO) and the like can be mentioned.

These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.
Of these, PGMEA, PGME, γ-butyrolactone or EL is preferably used.

  [2-4] Next, the patterned film is cured to obtain the protective film 70.

  In addition, the hardening process of the said film | membrane can be smoothly advanced by heating the patterned film | membrane, for example.

  The temperature for heating the film is preferably in the range of 150 to 400 ° C, more preferably in the range of 170 to 350 ° C. On the other hand, when considering the thermal effect on the semiconductor chip 20, it is preferably about 170 to 250 ° C.

  The heating time is preferably in the range of 1 to 60 minutes, and more preferably in the range of 10 to 30 minutes.

  The atmosphere for heating may be an air atmosphere, but is preferably an inert atmosphere such as nitrogen or a reduced pressure atmosphere. Thereby, hardening reaction can be advanced more reliably.

  The average film thickness of the protective film 70 is preferably about 1 to 20 μm, and more preferably about 5 to 10 μm. Thereby, the function as the protective film 70 described above can be surely exhibited.

  [3] Next, the constituent material of the adhesive layer 60 before curing is supplied onto the die pad 30 by using a commercially available discharge device such as a die bonder.

  [4] Next, the semiconductor chip 20 is placed on the die pad 30 with the surface on which the protective film 70 is provided on the die pad 30 so that the constituent material of the adhesive layer 60 before curing is interposed, and heated. To do. Thereby, the constituent material of the adhesive layer 60 before curing is cured, and the adhesive layer 60 composed of the cured product is formed. As a result, the semiconductor chip 20 is bonded onto the die pad (support) 30 via the adhesive layer 60.

  [5] Next, the conductive wire 22 is wired between the electrode pad 21 exposed from the protective film 70 and the lead 40 by wire bonding. Thereby, the electrode pad 21 and the lead 40 are electrically connected.

[6] Next, the mold part 50 is formed by, for example, transfer molding.
Thereafter, a resin-fixed tie bar is punched out from the lead frame, and a trim and foam process is performed to manufacture the semiconductor device 10.

<Protective film 70>
Next, the protective film 70 will be described.

  As described above, the protective film 70 is provided on the surface of the semiconductor chip 20 (semiconductor substrate), and contains a phenolic hydroxyl group-containing resin (an embodiment of the phenolic hydroxyl group-containing resin of the present invention) ( It is a cured film formed using the liquid material of the embodiment of the photosensitive resin composition of the present invention.

≪Phenolic hydroxyl group-containing resin≫
The phenolic hydroxyl group-containing resin according to this embodiment has a structure represented by the following formula (1a).

［式中、Ｘは、炭素数１〜３０の有機基であり、Ｙは、水素原子、アルキル基、シクロアルキル基またアリール基であり、Ｒは、それぞれ独立して、水酸基、ハロゲン原子、カルボキシル基、炭素数１〜２０の飽和または不飽和のアルキル基、炭素数１〜２０のアルキルエーテル基、炭素数３〜２０の飽和または不飽和の脂環式基、および炭素数６〜２０の芳香族構造を有する有機基からなる群から選ばれる一価の置換基であって、前記置換基はエステル結合、エーテル結合、アミド結合、またはカルボニル結合を介して結合していてもよい。また、ｐは０〜３の整数である。］

[Wherein X is an organic group having 1 to 30 carbon atoms, Y is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R is independently a hydroxyl group, a halogen atom or a carboxyl group. Group, saturated or unsaturated alkyl group having 1 to 20 carbon atoms, alkyl ether group having 1 to 20 carbon atoms, saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, and fragrance having 6 to 20 carbon atoms It is a monovalent substituent selected from the group consisting of organic groups having a group structure, and the substituent may be bonded via an ester bond, an ether bond, an amide bond, or a carbonyl bond. Moreover, p is an integer of 0-3. ]

  A photosensitive resin composition containing such a phenolic hydroxyl group-containing resin has excellent solubility in a developer. For this reason, when the protective film 70 is patterned into a target shape through photosensitivity / development processing, the protective film 70 with high dimensional accuracy can be obtained. In addition, since the occurrence of so-called development residue is suppressed, the occurrence of defects associated with the residue can be suppressed. Thereby, the highly reliable semiconductor device 10 can be realized.

  X in the above formula (1a) is an organic group having 1 to 30 carbon atoms, and X is bonded to the benzene ring via an ether bond. This is considered to be one of the factors.

  In addition, according to the phenolic hydroxyl group-containing resin having such a molecular structure, solubility in a developer can be ensured even when the number of the structures is large, for example, a polynuclear body having four or more nuclei. . For this reason, a photosensitive resin composition containing such a phenolic hydroxyl group-containing resin enables generation of a cured film having high mechanical strength derived from a polynuclear body, while developing due to the structure of X or an ether bond. It is possible to form a resin film showing good solubility in the liquid.

  X in the above formula (1a) is a monovalent organic group having 1 to 30 carbon atoms as described above. This organic group is a linear or branched monovalent hydrocarbon group and may contain at least one of oxygen, nitrogen, and silicon. X in the formula (1a) is an amino group (—NR—), an amide bond (—NHC (═O) —), an ester bond (—C (═O) —O—), a carbonyl group (—C (= O)-), an ether bond (-O-) and the like may be contained.

  Specific examples of the organic group according to X include an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an alkyloxyalkyl group having 4 to 12 carbon atoms. Is mentioned.

  Among these, examples of the alkyl group having 1 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group and the like. Further, for example, the hexyl group is not limited to a linear group such as an n-hexyl group, but is a branched one such as an isohexyl group, a sec-hexyl group, a tert-hexyl group, or a neohexyl group. Also good. This also applies to other alkyl groups. The carbon number of the alkyl group is preferably 6-20. When the carbon number is within this range, the chemical resistance of the cured product of the photosensitive resin composition becomes better.

  Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, and cycloundecyl. Group, cyclododecyl group and the like. The cycloalkyl group preferably has 6 to 10 carbon atoms. When the carbon number is within this range, the chemical resistance of the cured product of the photosensitive resin composition becomes better.

  Examples of the aryl group having 6 to 14 carbon atoms include phenyl group, benzyl group, styryl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group, 2-naphthyl group, 1 -Anthryl group, 2-anthryl group, 9-anthryl group, tosyl group, adamantyl group and the like can be mentioned. The aryl group preferably has 6 to 10 carbon atoms. When the carbon number is within this range, the chemical resistance of the cured product of the photosensitive resin composition becomes better.

  Examples of the alkyloxyalkyl group having 4 to 12 carbon atoms include 2-methoxyethyl group, (2-methoxyethoxy) -2-ethoxyethyl group, (2-methoxyethoxy) -2-ethoxy-2-ethoxy. An ethyl group etc. are mentioned. The carbon number of the alkyloxyalkyl group is preferably 4-8. When the carbon number is within this range, the elastic modulus of the cured product of the photosensitive resin composition becomes better.

  One or more hydrogen atoms contained in the organic group described above may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

  Moreover, since the molecular structure of an organic group will become small when carbon number of an organic group is less than the said lower limit, there exists a possibility that the solubility with respect to the developing solution of the photosensitive resin composition may fall. On the other hand, if the carbon number of the organic group exceeds the upper limit, excessive flexibility is imparted to the cured film of the photosensitive resin composition, and the mechanical strength of the protective film 70 may be reduced.

  Here, X in the above formula (1a) is preferably any one of a hexyl group, a cyclohexyl group, a methoxyethyl group, and a benzyl group. These hydrocarbon groups have an appropriate number of carbon atoms and relatively low reactivity. For this reason, the photosensitive resin composition containing the phenolic hydroxyl group containing resin which has such X shows especially favorable solubility with respect to a developing solution. On the other hand, since this hydrocarbon group hardly inhibits the polymerization reaction, a resin having an appropriate molecular weight is easily realized. Therefore, a good cured film can be obtained from the viewpoint of mechanical strength and chemical resistance. As a result, the protective film 70 with high dimensional accuracy and high reliability can be obtained.

  On the other hand, Y in the above formula (1a) is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

  Among these, examples of the alkyl group include an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group and the like. Further, for example, the hexyl group is not limited to a linear group such as an n-hexyl group, but is a branched one such as an isohexyl group, a sec-hexyl group, a tert-hexyl group, or a neohexyl group. Also good. This also applies to other alkyl groups. The carbon number of the alkyl group is preferably 1-20.

  Examples of the cycloalkyl group include cycloalkyl groups having 3 to 12 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, cycloheptyl group, cyclooctyl group, and cyclononyl group. , Cyclodecyl group, cycloundecyl group, cyclododecyl group and the like. The cycloalkyl group preferably has 6 to 10 carbon atoms.

  Moreover, as an aryl group, a C6-C14 aryl group is mentioned, For example, a phenyl group, a benzyl group, a styryl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group, Examples include 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, tosyl group, adamantyl group and the like. The aryl group preferably has 6 to 10 carbon atoms.

  Note that one or more hydrogen atoms contained in the above-described alkyl group, cycloalkyl group, and aryl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

  Here, Y in the above formula (1a) is preferably a hydrogen atom. Thereby, the photosensitive resin composition has high flexibility in the molecular structure. For this reason, particularly good solubility in the developer is obtained.

  The phenolic hydroxyl group-containing resin may contain a structure other than the structure represented by the above formula (1a). In this case, when the abundance ratio of the structure represented by the formula (1a) in the phenolic hydroxyl group-containing resin is 100 parts by mole, the other structure is preferably 90 parts by mole or less, and 50 parts by mole or less. Is more preferable, and it is further more preferable that it is 30 mol part or less. Thereby, the phenolic hydroxyl group-containing resin in which the function and effect exhibited by the structure represented by the above formula (1a) are sufficiently expressed is obtained.

  In addition, the phenolic hydroxyl group-containing resin according to this embodiment preferably has a structure represented by the following formula (1b).

［式中、Ｘは、炭素数１〜３０の有機基であり、Ｙは、水素原子、アルキル基、シクロアルキル基またはアリール基であり、Ｒは、それぞれ独立して、水酸基、ハロゲン原子、カルボキシル基、炭素数１〜２０の飽和または不飽和のアルキル基、炭素数１〜２０のアルキルエーテル基、炭素数３〜２０の飽和または不飽和の脂環式基、および炭素数６〜２０の芳香族構造を有する有機基からなる群から選ばれる一価の置換基であって、前記置換基はエステル結合、エーテル結合、アミド結合、またはカルボニル結合を介して結合していてもよい。また、ｐは０〜３の整数である。］

[Wherein X is an organic group having 1 to 30 carbon atoms, Y is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R is independently a hydroxyl group, a halogen atom or a carboxyl group. Group, saturated or unsaturated alkyl group having 1 to 20 carbon atoms, alkyl ether group having 1 to 20 carbon atoms, saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, and fragrance having 6 to 20 carbon atoms It is a monovalent substituent selected from the group consisting of organic groups having a group structure, and the substituent may be bonded via an ester bond, an ether bond, an amide bond, or a carbonyl bond. Moreover, p is an integer of 0-3. ]

  In the phenolic hydroxyl group-containing resin having the structure represented by the formula (1b), the organic group via the ether bond is located at the p-position (para-position) of the hydroxyl group, so that the physical properties and the like are more stable. .

  In particular, an organic group is bonded to the p-position of the hydroxyl group contained in the above formula (1b). For this reason, in the phenolic hydroxyl group-containing resin having the structure represented by the above formula (1b), the two o-positions (ortho positions) or the two m-positions (meta positions) of the hydroxyl groups serve as reaction points. It has a molecular structure extending in a shape. Such a molecular structure contributes to increasing the solubility in a developer while maintaining the mechanical strength of the cured film. That is, the photosensitive resin composition containing such a resin is imparted with excellent solubility in a developer, and high mechanical strength is imparted to the cured film.

  Further, the alkyl ether group contained in R in the above formula (1a) or (1b) is not particularly limited, but as an example, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy group , Heptoxy group, octoxy group and the like.

  In addition, the saturated or unsaturated alicyclic group contained in R in the aforementioned formula (1a) or formula (1b) is a monovalent containing a saturated or unsaturated carbocyclic ring having no aromaticity. Examples of the substituent include, but are not limited to, cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, and the like. Such as a cycloalkenyl group.

  Further, the organic group having an aromatic structure contained in R in the formula (1a) or the formula (1b) is not particularly limited as long as it is a monovalent substituent having a benzene ring. And the same aryl group as described above.

  In addition, these substituents may be directly bonded to the carbon atom constituting the benzene ring in the formula (1a) or (1b), and may have an ester bond, an ether bond, an amide bond, or a carbonyl bond. It may be bonded via.

  In addition, the phenolic hydroxyl group-containing resin according to this embodiment preferably has a structure represented by the following formula (1c).

［式中、Ｘは、炭素数１〜３０の有機基であり、Ｙは、水素原子、アルキル基、シクロアルキル基またはアリール基である。］

[Wherein, X is an organic group having 1 to 30 carbon atoms, and Y is a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. ]

  By including the structure represented by the above formula (1c) in which the main chain is bonded to the o-position of the hydroxyl group, the phenolic hydroxyl group-containing resin becomes more stable in properties and the like.

≪Method for synthesizing phenolic hydroxyl group-containing resin≫
Next, an example of a method for synthesizing the phenolic hydroxyl group-containing resin according to this embodiment will be described.

(Raw material preparation process)
As a monomer used as a raw material, for example, a phenol monomer represented by the following formula (2), an aldehyde monomer represented by the following formula (3a), a methylol monomer represented by the formula (3b), and a formula (3c) And a methoxyalkyl monomer represented by (3d).

［式中、Ｘは、炭素数１〜３０の有機基である。Ｒは、それぞれ独立して、水酸基、ハロゲン原子、カルボキシル基、炭素数１〜２０の飽和または不飽和のアルキル基、炭素数１〜２０のアルキルエーテル基、炭素数３〜２０の飽和または不飽和の脂環式基、および炭素数６〜２０の芳香族構造を有する有機基からなる群から選ばれる一価の置換基であって、前記置換基はエステル結合、エーテル結合、アミド結合、またはカルボニル結合を介して結合していてもよい。また、ｐは０〜３の整数である。］

[In formula, X is a C1-C30 organic group. R each independently represents a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, or a saturated or unsaturated group having 3 to 20 carbon atoms. And a monovalent substituent selected from the group consisting of an organic group having an aromatic structure having 6 to 20 carbon atoms, wherein the substituent is an ester bond, an ether bond, an amide bond, or a carbonyl group. It may be bonded via a bond. Moreover, p is an integer of 0-3. ]

［式中、Ｙは、水素原子、アルキル基、シクロアルキル基またはアリール基である。］

[Wherein Y represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. ]

_{HOCH 2 -Z-CH 2 OH (} 3b)
[In the formula, Z represents a divalent organic group which may be substituted. ]

_{H 3 COCH 2 -Z-CH 2} OCH 3 (3c)
[In the formula, Z represents a divalent organic group which may be substituted. ]

_{JCH 2 -Z-CH 2 J (} 3d)
[In the formula, Z represents a divalent organic group which may be substituted. J is a halogen atom. ]

  Among these, examples of the phenol monomer include 4-methoxyphenol, 4-ethoxyphenol, 4-propoxyphenol, 4-butoxyphenol, 4-pentyloxyphenol, 4-hexyloxyphenol, 4-heptyloxyphenol, 4- Octyloxyphenol, 4-nonyloxyphenol, 4-decyloxyphenol, hydroquinone monoethoxyethyl ether, 4- (2-methoxyethoxy) phenol, 4- (2-methoxyethoxy) -2-ethoxyphenol, 4- (2 -Methoxyethoxy) -2-alkoxyphenol such as 2-ethoxy-2-ethoxyphenol, 4-cyclohexyloxyphenol, cycloalkoxyphenol such as 4-cyclooctyloxyphenol, 4-benzi Oxy phenol, aryloxy phenol such as 4-tolyl oxy phenol. A plurality of monomers can be used in combination.

  On the other hand, as aldehyde monomers, for example, formaldehyde, acetaldehyde, butyraldehyde, acrolein, propionaldehyde, chloral, furfural, glyoxal, butyraldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, phenylacetaldehyde, tolualdehyde, salicylaldehyde These can be used, and one or more of these can be used in combination.

  Of these, formaldehyde is preferably used. Moreover, you may use formaldehyde and another aldehyde monomer together.

  Although the reaction ratio of a phenol monomer and an aldehyde monomer is suitably set according to each molecular structure, it is preferable that it is about 0.1-3.0 mol of aldehyde monomers with respect to 1 mol of phenol monomers as an example, 0 More preferably, it is about 3 to 2.0 mol. This makes it easy to control the molecular structure to the desired one.

  Examples of the methylol monomer include 2,2-dimethylolpentane, N, N′-dimethylolurea, dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,6-bis (hydroxymethyl) -p-cresol, 2 , 3-bis (hydroxymethyl) naphthalene, 4,4′-bis (hydroxymethyl) biphenyl, 4,4′-bis (hydroxymethyl) benzophenone, 4,4′-bis (hydroxymethyl) -2,2′- Bipyridine, 4,4′-bis (hydroxymethyl) phenylurea, 4,4′-bis (hydroxymethyl) phenylurethane, 4,4′-bis (hydroxymethyl) biphenyl, 2,2′-dimethyl-4,4 '-Bis (hydroxymethyl) biphenyl, 2,2-bis (4-hydroxymethylphenyl) propane, 1,8-bis ( Hydroxymethyl) anthracene and the like, and one or more of them can be used in combination.

  Of these, 2,6-bis (hydroxymethyl) -p-cresol is preferably used. Further, 2,6-bis (hydroxymethyl) -p-cresol and other methylol monomers may be used in combination.

  The reaction ratio between the phenol monomer and the methylol monomer is appropriately set according to the molecular structure, but as an example, it is preferably about 0.1 to 3.0 mol of methylol monomer per mol of phenol monomer. More preferably, it is about 3 to 2.0 mol. This makes it easy to control the molecular structure to the desired one.

  Z in the formula (3b) is not particularly limited as long as it is a divalent organic group which may be substituted. For example, an alkylene group having 1 to 10 carbon atoms and an arylene group having 6 to 30 carbon atoms are used. , An organic group containing a sulfonyl group, a carbonyl group, an ether bond, a sulfide bond, an amide bond, a urea bond and the like. Among these, some or all of the hydrogen atoms may be substituted with an alkyl group, aryl group, hydroxyl group, alkoxy group, carboxyl group, amino group, or halogen atom.

  Examples of the methoxymethyl monomer include 1,6-dimethoxyhexane, bis (2-methoxymethyl) adipate, 1,4-bis (methoxymethyl) benzene, and the like, one or more of these Can be used in combination.

  Of these, 1,4-bis (methoxymethyl) benzene is preferably used. Further, 1,4-bis (methoxymethyl) benzene and other methoxymethyl monomers may be used in combination.

The reaction ratio between the phenol monomer and the methoxymethyl monomer is appropriately set according to the molecular structure of each, but as an example, it is preferably about 0.1 to 3.0 mol of methoxymethyl monomer with respect to 1 mol of phenol monomer. More preferably, it is about 0.3 to 2.0 mol. This makes it easy to control the molecular structure to the desired one.
Z in the above formula (3c) is the same as Z in the above formula (3b).

  Examples of the haloalkyl monomer include compounds described in paragraph [0019] of JP 2012-251106 A, and one or more of these can be used in combination.

  Of these, bischloromethylbiphenyl is preferably used. Bischloromethylbiphenyl and other haloalkyl monomers may be used in combination.

The reaction ratio between the phenol monomer and the haloalkyl monomer is appropriately set according to the molecular structure, but as an example, it is preferably about 0.1 to 3.0 mol of the haloalkyl monomer with respect to 1 mol of the phenol monomer. More preferably, it is about 3 to 2.0 mol. This makes it easy to control the molecular structure to the desired one.
Note that Z in the above formula (3d) is the same as Z in the above formula (3b).

  Moreover, monomers other than the above may be added as necessary. The addition amount of monomers other than the above is appropriately set according to the abundance ratio of the structure represented by the formula (1a) in the phenolic hydroxyl group-containing resin.

  Examples of the monomer other than the above include various phenol derivatives. Specifically, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, Such as 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol Alkoxyphenol such as alkylphenol, methoxyphenol, 2-methoxy-4-methylphenol, alkenylphenol such as vinylphenol and allylphenol, aralkylphenol such as benzylphenol, alkoxycarbo such as methoxycarbonylphenol Arylphenol phenols such as ruphenol, benzoyloxyphenol, halogenated phenols such as chlorophenol, polyhydroxybenzenes such as catechol, resorcinol, pyrogallol, bisphenols such as bisphenol A and bisphenol F, α- or β-naphthol Of naphthol derivatives such as, p-hydroxyphenyl-2-ethanol, p-hydroxyphenyl-3-propanol, hydroxyalkylphenols such as p-hydroxyphenyl-4-butanol, hydroxyalkylcresols such as hydroxyethylcresol, bisphenol Alcoholic hydroxyl group-containing phenol derivatives such as monoethylene oxide adducts, bisphenol monopropylene oxide adducts, Carboxyl group-containing phenol derivatives such as hydroxyphenylacetic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylbutanoic acid, p-hydroxycinnamic acid, hydroxybenzoic acid, hydroxyphenylbenzoic acid, hydroxyphenoxybenzoic acid, diphenolic acid Is mentioned.

(Synthesis process)
Next, a phenol monomer and an aldehyde monomer (methylol monomer, methoxymethyl monomer or haloalkyl monomer) are reacted. This reaction is performed, for example, by mixing a phenol monomer and an aldehyde monomer (methylol monomer, methoxymethyl monomer, or haloalkyl monomer) at a temperature of about 60 to 140 ° C. in the presence of an acid catalyst. Thereafter, the solvent and residual monomer are removed under reduced pressure.

  Examples of the acid catalyst include oxalic acid, sulfuric acid, hydrochloric acid, organic sulfonic acid such as phenolsulfonic acid and p-toluenesulfonic acid, acetic acid hydrochloric acid, manganese acetate, and the like. Are used in combination.

Although the addition amount of an acid catalyst is not specifically limited, It is preferable that it is about 0.001-4.0 mol with respect to 1 mol of phenol monomers, and it is more preferable that it is about 0.003-2.0 mol. When the addition amount of the acid catalyst is less than the lower limit, the effect as a reaction catalyst may be impaired. On the other hand, when the addition amount of the acid catalyst exceeds the upper limit, an acid catalyst that does not contribute to the reaction is generated, and the addition effect may be diminished.
The phenolic hydroxyl group-containing resin is synthesized as described above.

  In addition, when the phenol monomer represented by the said Formula (2) and the aldehyde monomer represented by the said Formula (3a) are made to react, the structure represented by following formula (4a) will be obtained.

［式中、Ｘは、炭素数１〜３０の有機基であり、Ｙは、水素原子、アルキル基、シクロアルキル基またはアリール基である。また、Ｒは、それぞれ独立して、水酸基、ハロゲン原子、カルボキシル基、炭素数１〜２０の飽和または不飽和のアルキル基、炭素数１〜２０のアルキルエーテル基、炭素数３〜２０の飽和または不飽和の脂環式基、および炭素数６〜２０の芳香族構造を有する有機基からなる群から選ばれる一価の置換基であって、前記置換基はエステル結合、エーテル結合、アミド結合、またはカルボニル結合を介して結合していてもよい。また、ｐは０〜３の整数である。また、ｎは、４〜１５の整数であるのが好ましい。］

[Wherein, X is an organic group having 1 to 30 carbon atoms, and Y is a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. In addition, each R independently represents a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, a saturated or 3 to 20 carbon atoms. A monovalent substituent selected from the group consisting of an unsaturated alicyclic group and an organic group having an aromatic structure having 6 to 20 carbon atoms, wherein the substituent is an ester bond, an ether bond, an amide bond, Alternatively, they may be bonded via a carbonyl bond. Moreover, p is an integer of 0-3. Moreover, it is preferable that n is an integer of 4-15. ]

  The structure represented by the above formula (4a) includes the structure represented by the above formula (1a).

  Moreover, when the phenol monomer represented by the said Formula (2) and the monomer represented by the said Formula (3b), Formula (3c), or Formula (3d) are made to react, it represents with following formula (4b). A structure is obtained.

［式中、Ｘは、炭素数１〜３０の有機基である。また、Ｚは、置換されていてもよい二価の有機基である。また、Ｒは、それぞれ独立して、水酸基、ハロゲン原子、カルボキシル基、炭素数１〜２０の飽和または不飽和のアルキル基、炭素数１〜２０のアルキルエーテル基、炭素数３〜２０の飽和または不飽和の脂環式基、および炭素数６〜２０の芳香族構造を有する有機基からなる群から選ばれる一価の置換基であって、前記置換基はエステル結合、エーテル結合、アミド結合、またはカルボニル結合を介して結合していてもよい。また、ｐは０〜３の整数である。また、ｎは、４〜１５の整数であるのが好ましい。］

[In formula, X is a C1-C30 organic group. Z is an optionally substituted divalent organic group. In addition, each R independently represents a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 1 to 20 carbon atoms, a saturated or 3 to 20 carbon atoms. A monovalent substituent selected from the group consisting of an unsaturated alicyclic group and an organic group having an aromatic structure having 6 to 20 carbon atoms, wherein the substituent is an ester bond, an ether bond, an amide bond, Alternatively, they may be bonded via a carbonyl bond. Moreover, p is an integer of 0-3. Moreover, it is preferable that n is an integer of 4-15. ]

  The structure represented by the above formula (4b) includes the structure represented by the above formula (1a) (a structure in which Y is a hydrogen atom).

  In the above formulas (4a) and (4b), each of n is within the above range, whereby the phenolic hydroxyl group-containing resin realizes a photosensitive resin composition having appropriate solubility in the developer. It will be possible. In addition, the protective film 70 formed from a photosensitive resin composition containing such a phenolic hydroxyl group-containing resin has particularly excellent chemical resistance, and the balance between flexibility and rigidity is optimized. That is, a phenolic hydroxyl group-containing resin capable of realizing a photosensitive resin composition having appropriate solubility before curing, and having excellent chemical resistance and mechanical strength after curing can be obtained.

  The weight average molecular weight of the phenolic hydroxyl group-containing resin according to this embodiment synthesized in this way is preferably about 1,000 to 100,000, more preferably about 3,000 to 50,000. preferable. Thereby, the photosensitive resin composition containing such a phenolic hydroxyl group-containing resin has appropriate solubility in a developer. In addition, the protective film 70 formed from such a photosensitive resin composition has particularly excellent chemical resistance, and the balance between flexibility and rigidity is optimized.

  If the weight average molecular weight of the phenolic hydroxyl group-containing resin is below the lower limit, the chemical resistance and mechanical strength of the protective film 70 may be lowered depending on the molecular structure. On the other hand, when the weight average molecular weight of the phenolic hydroxyl group-containing resin exceeds the upper limit, the solubility of the photosensitive resin composition in the developer may be lowered depending on the molecular structure, and the flexibility of the protective film 70 may be reduced. There is a risk that peeling and the like are likely to occur.

  In addition, the phenolic hydroxyl group-containing resin according to the present embodiment preferably has, for example, Mw (weight average molecular weight) / Mn (number average molecular weight) of 1.5 to 5.0, preferably 1.5 to 3.5. More preferably. Mw / Mn is a degree of dispersion indicating the width of the molecular weight distribution. By setting Mw / Mn within the above range, for example, when forming the protective film 70 using a photosensitive resin composition containing a phenolic hydroxyl group-containing resin, pattern deformation during curing can be suppressed, and patterning can be performed. Can improve the accuracy.

  The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are calculated from, for example, a standard polystyrene (PS) calibration curve obtained by GPC (Gel Permeation Chromatography) measurement. Polystyrene equivalent value is used. The measurement conditions are, for example, as follows.

-Gel permeation chromatography device HLC-8320GPC manufactured by Tosoh Corporation
Column: Tosoh Corporation TSK-GEL Supermultipore HZ-M
-Detector: RI detector for liquid chromatogram-Measurement temperature: 40 ° C
・ Solvent: Tetrahydrofuran (THF)
Sample concentration: 2.0 mg / ml

  The phenolic hydroxyl group-containing resin according to this embodiment has sufficient solubility in a developer as, for example, a positive photosensitive resin composition or a negative photosensitive resin composition, but the dissolution rate is 50 nm / second. It is preferably 2000 nm / second or less. Thereby, the efficiency of the developing process with the developer can be sufficiently increased, and the generation of residues after development can be sufficiently suppressed.

The dissolution rate is measured as follows.
First, a phenolic hydroxyl group-containing resin is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution having a solid content of 25% by mass.

Next, the prepared solution is spin-coated on a silicon wafer and then dried at 100 ° C. for 6 minutes to obtain a polymer film.
Next, this polymer film is immersed in a solvent (developer) and allowed to stand for 30 seconds.

  Next, the polymer film is taken out and rinsed with pure water, and the presence or absence of a polymer film residue is visually confirmed. Then, the dissolution rate is calculated by measuring the time required until the polymer film disappears.

  Further, the synthesized phenolic hydroxyl group-containing resin may contain low molecular weight components such as monomers and oligomers that have not been polymerized. Examples of such a low molecular weight component include monomers represented by the aforementioned formulas (2) and (3).

  In that case, the content of the low molecular weight component is preferably appropriately controlled so that the peak area at a molecular weight of 1000 or less is 2% or less in the molecular weight distribution curve obtained by GPC. Thereby, when forming the protective film 70 using the photosensitive resin composition containing phenolic hydroxyl group containing resin, for example, the deformation | transformation of the pattern at the time of hardening can be suppressed and the precision of patterning can be improved.

  In addition, in the plurality of structures included in the phenolic hydroxyl group-containing resin according to the present embodiment, the bonding position of the main chain to the benzene ring is preferably the same as each other, but may be different from each other.

  Moreover, in the plurality of contained structures, the bonding positions of (—O—X) with respect to the benzene ring are preferably the same as each other, but may be different from each other.

  In the plurality of structures included, X is preferably the same organic group as each other, but may be different from each other. Similarly, Y is preferably the same as each other, but may be different from each other.

  Further, in the plurality of included structures, Z is preferably the same as each other, but may be different from each other.

≪Photosensitive resin composition≫
The photosensitive resin composition which concerns on this embodiment has the phenolic hydroxyl group containing resin which concerns on this embodiment, the crosslinking agent which can be bridge | crosslinked with this phenolic hydroxyl group containing resin, and a photosensitive agent. Such a photosensitive resin composition is excellent in solubility in a developing solution due to the action and effect of the phenolic hydroxyl group-containing resin described above, and can form a protective film 70 (cured film) with high dimensional accuracy by good patterning. To.

(Phenolic hydroxyl group-containing resin)
Although the photosensitive resin composition which concerns on this embodiment has phenolic hydroxyl-containing resin mentioned above, the content rate is 20-20, when the total solid of the photosensitive resin composition is 100 mass parts. The amount is preferably 90 parts by mass, and more preferably 30 to 80 parts by mass. Thereby, the photosensitive resin composition can fully exhibit the characteristics of the phenolic hydroxyl group-containing resin described above.

(Crosslinking agent)
The photosensitive resin composition according to the present embodiment has a crosslinking agent capable of crosslinking with the phenolic hydroxyl group-containing resin. Thereby, sclerosis | hardenability can be improved and the mechanical strength of a cured film like the protective film 70 can be raised.

  Examples of the crosslinking agent include melamine type, substituted urea type, or polymer type thereof.

  Further, as the cross-linking agent, those having at least two cross-linking substituents such as a methylol group and an alkoxymethyl group are preferably used, and a nitrogen-containing compound having 2 to 4 nitrogen atoms substituted with the cross-linking substituents Is more preferably used.

  Examples of such nitrogen-containing compounds include hexamethoxymethyl melamine (trade names: MX-30HM, MX-390, MX-100LM, manufactured by Sanwa Chemical Co., Ltd.), tetramethoxymethyl benzoguanamine, 1, 3, 4 , 6-Tetrakis (methoxymethyl) glycoluril (trade name: MX-270, manufactured by Sanwa Chemical Co., Ltd.), 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6 -Tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) urea, etc. These may be used, and one or more of these may be used in combination.

  Other aromatic compounds substituted with a methylol group or a methoxymethyl group include, for example, 1-hydroxybenzene-2,4,6-trimethanol, 3,3 ′, 5,5′-tetrakis (hydroxymethyl) -4 , 4′-dihydroxybiphenyl, 5,5 ′-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 2,2- Dimethoxymethyl-4-t-butylphenol, 3,3 ′, 5,5′-tetramethoxymethyl-4,4′-dihydroxybiphenyl, bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methane, bis (4-Hydroxy-3-hydroxymethyl-5-methylphenyl) methane, 5,5 ′-(1-methylethylidene) bis (2- Dorokishi 1,3 benzenedimethanol), whether employed singly or in combination of two or more of them.

  Although the content rate of a crosslinking agent is not specifically limited, It is preferable that it is about 1-80 mass parts with respect to 100 mass parts of phenolic hydroxyl group containing resin, and it is more preferable that it is about 10-60 mass parts. If the content of the crosslinking agent is lower than the lower limit value or higher than the upper limit value, the chemical resistance of the cured film such as the protective film 70 may be lowered.

  In addition, what is necessary is just to add a crosslinking agent as needed, for example, when phenolic hydroxyl group containing resin has self-crosslinking property, addition may be abbreviate | omitted.

(Photosensitive agent)
The photosensitive resin composition according to the present embodiment has a photosensitive agent. The patterning method can be selected from a positive type and a negative type.

  In the case of the positive type, the film obtained by drying the photosensitive resin composition is selectively irradiated with light, so that the solubility of the film located in the light irradiation region in the alkaline aqueous solution can be reduced. Compared to the solubility of the film located in the non-irradiated region in the alkaline aqueous solution, the film can be improved. Therefore, alkali solubility can be imparted to the photosensitive resin composition, and a positive photosensitive resin composition can be provided.

  In the case of the negative type, the film located in the light irradiation region is insoluble in the organic solvent by applying a heating process after selectively irradiating the film obtained by drying the photosensitive resin composition. Thus, the film located in the non-irradiated region remains soluble in the organic solvent. Therefore, the organic resin insolubility can be imparted to the photosensitive resin composition, and a negative photosensitive resin composition can be provided.

  As the photosensitive agent, in the case of a positive photosensitive resin composition, a photoacid generator that generates an acid by absorbing light energy can be used.

  Specifically, diazoquinone compound; diaryl iodonium salt; 2-nitrobenzyl ester compound; N-iminosulfonate compound; imidosulfonate compound; 2,6-bis (trichloromethyl) -1,3,5-triazine compound; dihydropyridine compound Etc.

  Among these compounds, photosensitive diazoquinone compounds are preferably used. Since such a compound is most excellent in sensitivity and resolution in the wavelength range of actinic radiation mainly used for exposure, the protective film 70 can be formed with excellent patterning accuracy.

  Examples of the photosensitive diazoquinone compound include esters of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid. These may be used alone or in combination of two or more.

  In addition, as a specific structure of these compounds, Formula (B10)-Formula (B16) described in Unexamined-Japanese-Patent No. 2013-174843 is mentioned, for example.

  On the other hand, in the case of a negative photosensitive resin composition, a photoacid generator is used as a photosensitizer, and further a crosslinker that crosslinks a polymer by the action of an acid.

  Specifically, any acid may be used as long as it generates an acid by absorbing light energy. For example, triarylsulfonium salt, triphenylsulfonium trifluoromethanesulfonate, tris (4-t-butylphenyl) sulfonium-trifluoromethane. Sulfonium salts such as sulfonate; diazonium salts such as p-nitrophenyldiazonium hexafluorophosphate; ammonium salts; phosphonium salts; iodonium salts such as diphenyliodonium trifluoromethanesulfonate, (triccumyl) iodonium-tetrakis (pentafluorophenyl) borate; quinonediazides , Diazomethanes such as bis (phenylsulfonyl) diazomethane; 1-phenyl-1- (4-methylphenyl) sulfonyloxy Sulfonic acid esters such as -1-benzoylmethane and N-hydroxynaphthalimide-trifluoromethanesulfonate; disulfones such as diphenyldisulfone; tris (2,4,6-trichloromethyl) -s-triazine, 2- (3 And compounds such as triazines such as 4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -s-triazine. These photoacid generators can be used alone or in combination.

  Although the content rate of a photosensitive agent is not specifically limited, It is preferable that it is about 1-50 mass parts with respect to 100 mass parts of phenolic hydroxyl group containing resin, It is more preferable that it is about 5-40 mass parts, 8- More preferably, it is about 30 parts by mass. Thereby, a difference in solubility in the developer can be reliably developed between the light irradiation region (exposure portion) and the light non-irradiation region (non-exposure portion).

  The photosensitive resin composition which concerns on this embodiment may have the acid generator which generates an acid with heat other than a photosensitive agent as needed. By including such an acid generator, the crosslinking reaction between the phenolic hydroxyl group-containing resin and the crosslinking agent can be promoted by heating the photosensitive resin composition.

  Although the content rate of an acid generator is not specifically limited, It is preferable that it is 3 mass parts or less with respect to 100 mass parts of crosslinking agents.

  Examples of thermal acid generators that generate acid by heat include SI-45L, SI-60L, SI-80L, SI-100L, SI-110L, SI-150L, SI-200 (Sanshin Chemical Industry Co., Ltd.) Aromatic sulfonium salts such as

  In addition, when the total solid content of a resin composition is 100 mass parts, it is preferable that the content rate of an acid generator is 0.1-5 mass parts.

(Surfactant)
The photosensitive resin composition according to this embodiment may have a surfactant as necessary.

  As the surfactant, for example, one having a crosslinkable group is used. Examples of the crosslinkable group contained in the surfactant include those that crosslink with a phenolic hydroxyl group-containing resin or a crosslinker, or that crosslink with a surfactant alone. In particular, the crosslinkable group is preferably one that causes a crosslinking reaction by light or heat, and examples thereof include a (meth) acryloyl group and a vinyl group. In this case, it is possible to perform crosslinking more efficiently by further including a radical polymerization initiator such as azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO) in the photosensitive resin composition. is there.

  Thus, the coating property of the photosensitive resin composition can be improved by adding a surfactant having a crosslinkable group to the photosensitive resin composition. Furthermore, by using a surfactant having a crosslinkable group, the surfactant can cause a crosslinking reaction to improve the chemical resistance of the cured film of the photosensitive resin composition.

  The surfactant having a crosslinkable group is preferably a compound containing a fluorine group (for example, a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as a main skeleton. Such a surfactant is collected on the surface of the coating film of the photosensitive resin composition by having a fluorine group or a silanol group or having a siloxane bond as a main skeleton. And since it will carry out a crosslinking reaction on the surface of the film | membrane of the photosensitive resin composition, the chemical resistance of the cured film of the photosensitive resin composition can be improved more reliably. Such an effect can be particularly prominent by using a surfactant having a fluorine group.

The surfactant having a crosslinkable group may be any of a nonionic surfactant, a cationic surfactant, and an anionic surfactant, but is a nonionic surfactant from the viewpoint of the stability of the photosensitive resin composition. It is preferable. For example, the surfactant having a crosslinkable group is a nonionic surfactant, and preferably has a polyoxyalkylene chain as a hydrophilic group. Examples of the polyoxyalkylene chain may include those represented by (OR) x, wherein R is an alkylene chain having 2 to 4 carbon atoms, and —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ — , —CH (CH ₃ ) CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, or —CH (CH ₃ ) CH (CH ₃ ) — is preferable. Note that x is a positive integer, preferably an integer of 2 to 50, and more preferably an integer of 3 to 30.

  Moreover, you may make it use together the surfactant which does not have a crosslinkable group with the surfactant which has a crosslinkable group. Thereby, smoothing of a cured film can be aimed at and generation | occurrence | production of the crack of a cured film can be suppressed.

  The surfactant having no crosslinkable group may be any of a nonionic surfactant, a cationic surfactant, and an anionic surfactant. From the viewpoint of the stability of the photosensitive resin composition, the nonionic surfactant is used. It is preferable that The surfactant having no crosslinkable group is preferably a compound containing a fluorine group or a silanol group or a compound having a siloxane bond as a main skeleton from the viewpoint of smoothing the film surface. Such a surfactant having a fluorine group or a silanol group or having a siloxane bond as a main skeleton has a high surface tension reducing ability, so that the film surface can be smoothed.

  As mentioned above, although it explained in full detail about each component of the photosensitive resin composition, a photosensitive resin composition is a base generator, a crosslinking catalyst, antioxidant, a filler, a sensitizer, an adhesive improvement agent etc. as needed. The additive may be included.

  Moreover, the photosensitive resin composition may contain the solvent which melt | dissolves or disperse | distributes the component mentioned above uniformly. Examples of such solvents include propylene glycol methyl ether acetate, dimethylformamide, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, dioxane, cyclohexanone, ethyl acetate, N-methyl-pyrrolidinone, One or a combination of two or more of these is used.

<< Hardened product of photosensitive resin composition >>
The photosensitive resin composition which concerns on this embodiment hardens | cures through the hardening process which is illustrated below, for example, and produces | generates hardened | cured material. This cured product preferably has the following physical properties.

(Glass transition temperature and thermal expansion coefficient)
First, the photosensitive resin composition varnished with propylene glycol methyl ether acetate (PGMEA) is passed through a filter having a pore diameter of 0.5 μm.

  Next, the photosensitive resin composition passed through the filter is applied to a silicon wafer or the like, and the obtained coating film is dried by heating at 100 ° C. for 6 minutes.

  Next, the temperature in the clean oven is maintained at 30 ° C., and a silicon wafer provided with a dried coating film is placed inside.

Next, the temperature is raised to 200 ° C. at a rate of 5 ° C. per minute, and then held for 60 minutes, and then lowered to 80 ° C. at a rate of 5 ° C. per minute.
A cured film having a thickness of 10 μm is obtained as described above.
A test piece having a width of 5 mm and a length of 10 mm or more is cut out from the cured film.

  Next, the glass transition temperature Tg and linear expansion of this test piece were measured using a thermomechanical analysis (TMA) apparatus under the conditions of a starting temperature of 30 ° C., a measurement temperature range of 30 to 400 ° C., and a heating rate of 5 ° C./min. The coefficient CTE is measured.

  The cured product of the photosensitive resin composition according to this embodiment preferably has a glass transition temperature Tg of 190 ° C. or higher, and more preferably 210 ° C. or higher. The cured product of such a photosensitive resin composition has a sufficiently high mechanical strength even at high temperatures. For this reason, the more reliable protective film 70 is obtained.

  Further, the cured product of the photosensitive resin composition according to this embodiment preferably has a thermal expansion coefficient of −50 to 150 ppm / ° C., and more preferably −30 to 100 ppm / ° C. Since such a cured product of the photosensitive resin composition has a small difference in thermal expansion from a semiconductor material such as silicon, for example, warpage of the semiconductor chip 20 and defects due to thermal stress can be suppressed.

(5% thermal weight loss temperature)
First, a cured film is obtained in the same manner as the evaluation of the glass transition temperature.
A test piece having a width of 10 mm and a length of 60 mm or more is cut out from the cured film.

  Next, about this test piece, 5% thermogravimetric decrease temperature Td5 is measured using a differential thermothermal weight simultaneous measurement apparatus (TG / DTA).

  The cured product of the photosensitive resin composition according to the present embodiment preferably has a 5% thermal weight loss temperature Td5 of 300 ° C. or higher, and more preferably 320 ° C. or higher. As a result, a weight reduction due to thermal decomposition or the like hardly occurs even at a high temperature, and a cured product having excellent heat resistance can be obtained. For this reason, the protective film 70 excellent in durability under a high temperature environment is obtained.

(Tensile strength, tensile modulus and tensile elongation)
First, a cured film is obtained in the same manner as the evaluation of the glass transition temperature.
A test piece having a width of 10 mm and a length of 60 mm or more is cut out from the cured film.

  Next, the test piece is subjected to a tensile test using a tensile tester. The test conditions are a tensile speed of 0.05 mm / min, a temperature of 23 ° C., and a relative humidity of 55%.

  And a tensile strength, a tensile elasticity modulus, and a tensile elongation rate are computed from the result of a tension test. In addition, about a measurement result, it is set as the average value of the measured value obtained from five or more test pieces, respectively.

  The cured product of the photosensitive resin composition according to this embodiment preferably has a tensile strength of 20 MPa or more, and more preferably 30 to 300 MPa. Thereby, the protective film 70 having sufficient mechanical strength and excellent durability can be obtained.

  Moreover, it is preferable that the cured | curing material of the photosensitive resin composition which concerns on this embodiment is 0.5 GPa or more in tensile elasticity modulus, and it is more preferable that it is 1-5 GPa. Thereby, the protective film 70 having sufficient mechanical strength and excellent durability can be obtained.

  Further, the cured product of the photosensitive resin composition according to the present embodiment preferably has a tensile elongation of 1% or more, more preferably 5% or more, and further preferably 10 to 50%. . Thereby, the hardened | cured material like the protective film 70 excellent in shape followability is obtained. As a result, the protective film 70 becomes more difficult to peel off.

  The physical properties as described above are the same as those described above for the cured product in which the maximum temperature during curing is reduced from 200 ° C to 180 ° C. Even when cured at such a relatively low temperature, the photosensitive resin composition according to the present embodiment can produce a cured product having excellent mechanical properties. For this reason, the thermal load applied to the semiconductor chip 20 and the like at the time of curing can be further reduced, which can contribute to the improvement of the reliability of the semiconductor chip 20. Moreover, since the thermal expansion coefficient is reduced along with the suppression of the thermal load, the occurrence of defects due to stress concentration is also suppressed.

(chemical resistance)
First, the photosensitive resin composition varnished with propylene glycol methyl ether acetate is passed through a filter having a pore diameter of 0.5 μm.

Next, the photosensitive resin composition passed through the filter is applied to a silicon wafer or the like, and the obtained coating film is dried.
Drying is performed by heating on a hot plate at 100 ° C. for 136 seconds.

Next, the dried coating film is immersed in an alkali developer (tetramethylammonium hydroxide aqueous solution having a concentration of 0.5% by mass) and left to stand for 90 seconds.
Next, the coating film is taken out and rinsed with pure water.

Next, ultraviolet rays are exposed at 300 mJ / cm ² and then heated in an oven at 230 ° C. for 60 minutes.
The film thickness of the coating film after heating is measured, and this is defined as t1.

  Next, the heated coating film is immersed in a chemical and left to stand for a predetermined time. Examples of chemicals include N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), tetramethylammonium hydro hydride having a concentration of 2.38% by mass Examples thereof include an aqueous oxide (TMAH) solution.

Next, the coating film is taken out, the film thickness is measured, and this is defined as t2.
And (t1-t2) / t1 * 100 is calculated and this is made into film thickness change rate (%).

  The film thickness change rate when the cured product of the photosensitive resin composition according to this embodiment is brought into contact with N-methylpyrrolidone (NMP) at 60 ° C. for 10 minutes is preferably 40% or less, and 30% or less. It is more preferable that Thereby, even when the protective film 70 is subjected to the step of being immersed in N-methylpyrrolidone, the film thickness is hardly reduced. For this reason, the protective film 70 which can maintain a function even after being subjected to such a process is obtained.

  Further, the film thickness change rate when the cured product of the photosensitive resin composition according to this embodiment is brought into contact with dimethyl sulfoxide (DMSO) at 60 ° C. for 10 minutes is preferably 30% or less, and 20% or less. It is more preferable that Thereby, even when the protective film 70 is subjected to the step of being immersed in dimethyl sulfoxide, the film thickness is hardly reduced. For this reason, the protective film 70 which can maintain a function even after being subjected to such a process is obtained.

  The rate of change in film thickness when the cured product of the photosensitive resin composition according to this embodiment is brought into contact with propylene glycol monomethyl ether (PGME) at 25 ° C. for 30 minutes is preferably 20% or less. % Or less is more preferable. Thereby, even when the protective film 70 is subjected to a step of being immersed in propylene glycol monomethyl ether, the film thickness is hardly reduced. For this reason, the protective film 70 which can maintain a function even after being subjected to such a process is obtained.

  Further, the film thickness change rate when the cured product of the photosensitive resin composition according to the present embodiment is brought into contact with propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C. for 30 minutes is preferably 20% or less, More preferably, it is 10% or less. Thereby, even when the protective film 70 is subjected to the step of being immersed in propylene glycol monomethyl ether acetate, the film thickness is hardly reduced. For this reason, the protective film 70 which can maintain a function even after being subjected to such a process is obtained.

  In addition, when the cured product of the photosensitive resin composition according to this embodiment is brought into contact with an aqueous tetramethylammonium hydroxide (TMAH) solution having a concentration of 2.38% by mass at 25 ° C. for 15 minutes, the film thickness change rate is 15 % Or less is preferable, and 10% or less is more preferable. Thereby, even when the protective film 70 is subjected to the step of being immersed in tetramethylammonium hydroxide, the film thickness is hardly reduced. For this reason, the protective film 70 which can maintain a function even after being subjected to such a process is obtained.

  In addition to the protective film 70 (passivation film) described above, the cured product of the photosensitive resin composition according to the present embodiment includes, for example, a semiconductor buffer coat, a rewiring layer, an α-ray prevention film, an interlayer insulating film, a photo It can be applied to photosensitive coating materials (coating layers) for various semiconductors such as resists.

  Among these, permanent films such as a semiconductor buffer coat, a rewiring layer, an α-ray prevention film, and an interlayer insulating film are required to have durability and mechanical strength for protecting the semiconductor chip 20. From this point of view, the photosensitive coating material including the cured product of the photosensitive resin composition according to the present embodiment can protect the semiconductor chip 20 over a long period of time when used as a permanent film, and is reliable. This contributes to the realization of a semiconductor device 10 having a high level.

<Electronic equipment>
The electronic apparatus according to the present embodiment includes the semiconductor device according to the present embodiment described above.

  Since such a semiconductor device includes a protective film having excellent chemical resistance, it is highly reliable. For this reason, high reliability is also provided to the electronic apparatus according to the present embodiment.

  The electronic device according to the present embodiment is not particularly limited as long as it includes such a semiconductor device. For example, the electronic device is a communication device such as a mobile phone, a smartphone, a tablet terminal, a personal computer, a server, or a router. Examples of such devices include in-vehicle devices such as devices, vehicle control computers, and car navigation systems.

  As mentioned above, although this invention was demonstrated based on embodiment of illustration, this invention is not limited to these.

  For example, the phenolic hydroxyl group-containing resin, the photosensitive resin composition, the semiconductor device, and the electronic device of the present invention may be those obtained by adding arbitrary elements to the embodiment.

  In addition to semiconductor devices, the photosensitive resin composition also applies to, for example, MEMS (Micro Electro Mechanical Systems) and various sensor structure forming materials, liquid crystal display devices, and structure forming materials for display devices such as organic EL devices. Is possible.

  The package form of the semiconductor device is not limited to the QFP type semiconductor package, but is a DIP (Dual In-line Package) type, an SOP (Small Out-line Package) type, and an LF-CSP (Lead Frame Chip Scale Package). Or a BGA (Ball Grid Array) type semiconductor package.

Next, specific examples of the present invention will be described.
1. Synthesis of phenolic hydroxyl group-containing resin (Synthesis Example 1)
[1] First, in a flask equipped with a condenser and a stirrer, 4-hexyloxyphenol (manufactured by Seiko Chemical) as a phenol monomer, formaldehyde (manufactured by Tokyo Chemical Industry) as an aldehyde monomer, and p-toluenesulfone as an acid catalyst The acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in γ-butyrolactone (GBL) (manufactured by Mitsubishi Chemical Corporation) as a solvent and stirred. In addition, the compounding ratio of each raw material is as shown in Table 1.

  [2] Next, after the atmosphere in the flask was replaced with nitrogen, the temperature of the solution was increased to 70 ° C. while stirring, and then maintained for 7 hours. Thereby, a reaction solution was obtained.

  [3] Next, the obtained reaction solution was dropped into an aqueous acetone solution over 5 minutes while stirring. The aqueous acetone solution was prepared so as to have a mass ratio of water / acetone = 9/1.

  [4] Next, the acetone aqueous solution to which the reaction solution was dropped was allowed to stand for 30 minutes, and then the supernatant was removed and the precipitate was collected. And the collect | recovered deposit was heated up to 60 degreeC under vacuum pressure reduction, and was then dried over 48 hours. Thereby, a polymer (phenolic hydroxyl group-containing resin) was obtained.

(Synthesis Example 2)
[1] First, in a flask equipped with a condenser and a stirrer, 4-hexyloxyphenol as a phenol monomer, 2,6-bis (hydroxymethyl) -p-cresol (manufactured by Tokyo Chemical Industry) as a methylol monomer, and As an acid catalyst, p-toluenesulfonic acid was dissolved in γ-butyrolactone (GBL) as a solvent and stirred. In addition, the compounding ratio of each raw material is as shown in Table 1.

  [2] Next, after the atmosphere in the flask was replaced with nitrogen, the temperature of the solution was raised to 70 ° C. while stirring, and then maintained for 6 hours. Thereby, a reaction solution was obtained.

  [3] Next, the obtained reaction solution was dropped into an aqueous acetone solution over 5 minutes while stirring. The aqueous acetone solution was prepared so as to have a mass ratio of water / acetone = 9/1.

  [4] Next, the acetone aqueous solution to which the reaction solution was dropped was allowed to stand for 30 minutes, and then the supernatant was removed and the precipitate was collected. And the collect | recovered deposit was heated up to 60 degreeC under vacuum pressure reduction, and was then dried over 48 hours. Thereby, a polymer (phenolic hydroxyl group-containing resin) was obtained.

(Synthesis Examples 3 to 8)
A polymer was obtained in the same manner as in Synthesis Example 2 except that the raw materials and the blending ratio thereof were changed as shown in Table 1.

(Comparative Synthesis Examples 1 to 7)
An attempt was made to obtain a polymer in the same manner as in Synthesis Example 1 or 2 except that the raw materials and the blending ratio thereof were changed as shown in Table 1.

  However, in some comparative synthesis examples, since the synthesized product was insolubilized (gelled) in the solvent, the polymer could not be deposited.

2. 2. Evaluation of phenolic hydroxyl group-containing resin 2.1 Evaluation of molecular weight From the calibration curve of standard polystyrene (PS) obtained by GPC measurement, the polymer obtained in each synthesis example and the polymer obtained in each comparative synthesis example could be precipitated. The weight average molecular weight was determined from the molecular weight distribution curve of the calculated polystyrene conversion value.
The measurement results are shown in Table 1.

2.2 Evaluation of degree of dispersion About the polymer obtained in each synthesis example and each of the comparative synthesis examples where the polymer could be precipitated, the polystyrene conversion value obtained from the calibration curve of standard polystyrene (PS) obtained by GPC measurement From the molecular weight distribution curve, the weight average molecular weight Mw and the number average molecular weight Mn were determined.

Next, the degree of dispersion defined by Mw / Mn was calculated.
The calculation results are shown in Table 1.

2.3 Evaluation of solubility in solvent About the polymer obtained in each synthesis example and each of the comparative synthesis examples, the polymer could be precipitated and dissolved in propylene glycol monomethyl ether acetate (PGMEA), and the solid content was 25% by mass. A solution was prepared.
Next, the prepared solution was passed through a filter having a pore size of 0.5 μm.

Next, the solution passed through the filter was spin-coated on a silicon wafer, and then dried at 100 ° C. for 6 minutes to obtain a polymer film.
Next, the obtained polymer film was immersed in the following solvents and allowed to stand for 30 seconds.

<Solvent used for evaluation>
・ Acetone ・ Propylene glycol monomethyl ether (PGME)
・ Propylene glycol monomethyl ether acetate (PGMEA)
・ Γ-Butyrolactone (GBL)
・ N-methylpyrrolidone (NMP)
・ Tetrahydrofuran (THF)

  Next, the polymer film was taken out and rinsed with pure water, and the presence or absence of a polymer film residue was visually confirmed. And the dissolution rate with respect to each solvent was computed by measuring the time required until the polymer film disappeared.

  And the solubility with respect to each solvent was evaluated in light of the following dissolution criteria for the calculated dissolution rate.

<Evaluation criteria for solubility in each solvent>
○: Dissolution rate is 50 nm / second or more and 2000 nm / second or less Δ: Dissolution rate is less than 50 nm / second or more than 2000 nm / second ×: Not dissolved at all Evaluation results are shown in Table 1.

  As is apparent from Table 1, it was confirmed that the polymers obtained in the respective synthesis examples had sufficient solubility in the solvent.

On the other hand, the polymers obtained in Comparative Synthesis Examples 4, 5, and 7 were not sufficiently soluble.
Moreover, since the synthesized products obtained in Comparative Synthesis Examples 1, 2, 3, and 6 were gelled, the molecular weight could not be measured.

3. Preparation of photosensitive resin composition (Example 1)
The polymer of Synthesis Example 1, 1,3,4,6-tetrakis (methoxymethyl) glycoluril (trade name: MX-270, manufactured by Sanwa Chemical Co., Ltd.) as a crosslinking agent, and the following formula (17) as a photosensitive agent The compound represented and RS-75 manufactured by DIC Corporation as a surfactant were each dissolved in γ-butyrolactone (GBL) as a solvent, and passed through a filter having a pore size of 0.5 μm. Thereby, a photosensitive resin composition was obtained. In addition, the blending ratio of each raw material is as shown in Table 2.

［式中、Ｑは、水素原子または下記式（１８）である。］

[In formula, Q is a hydrogen atom or following formula (18). ]

(Examples 2 to 10)
A photosensitive resin composition was obtained in the same manner as in Example 1 except that the raw materials and the blending ratio thereof were changed as shown in Table 2.

  “CPI-200K” in Table 2 is a photosensitizer CPI-200K manufactured by San Apro Co., Ltd.

(Comparative Examples 1-4)
A photosensitive resin composition was obtained in the same manner as in Example 1 except that the raw materials and the blending ratio thereof were changed as shown in Table 2.

4). 4. Evaluation of photosensitive resin composition 4.1 Evaluation of patterning property 4.1.1 Positive patterning property [1] First, the photosensitive resin composition of each example and each comparative example was spin-coated on a silicon wafer. And dried at 120 ° C. for 3 minutes to obtain a dry film having a film thickness of 9.0 to 10.0 μm.

  [2] Next, irradiation was performed by changing the exposure amount using an i-line stepper (Nikon Corporation NSR-4425i) through a positive pattern mask.

  [3] Next, using an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 2.38% by mass at 25 ° C. as a developer, the exposed portion is dissolved and removed by performing paddle development, and then rinsed with pure water. did. The film thickness after rinsing was 7.0 to 8.0 μm.

  [4] Next, whether or not patterning could be performed was visually confirmed, and positive patterning property was evaluated in light of the following evaluation criteria.

<Positive patterning evaluation criteria>
◯: A pattern could be obtained by dissolving the exposed area. ×: A pattern could not be obtained due to total dissolution or insolubility.

4.1.2 Negative patterning properties [1] First, the photosensitive resin compositions of the respective examples and comparative examples were spin-coated on a silicon wafer and then dried at 120 ° C. for 3 minutes to obtain a film thickness of 9.0. A dry film of ˜10.0 μm was obtained.

  [2] Next, irradiation was performed by changing the exposure amount using an i-line stepper (NSR-4425i, manufactured by Nikon Corporation) through a negative pattern mask. Thereafter, heating was performed at 100 ° C. for 3 minutes.

  [3] Next, using propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C. as a developing solution, paddle development was performed to dissolve and remove the unexposed portion, followed by rinsing with isopropyl alcohol (IPA). The film thickness after rinsing was 9.0 to 10.0 μm.

  [4] Next, it was visually confirmed whether or not patterning was possible, and negative patterning property was evaluated in light of the following evaluation criteria.

<Evaluation criteria for negative patterning>
○: A pattern could be obtained by dissolving the unexposed area. ×: A pattern could not be obtained due to total dissolution or insolubility.

4.2 Evaluation of glass transition temperature and thermal expansion coefficient The glass transition temperature and the thermal expansion coefficient (linear expansion coefficient) of the cured films of the photosensitive resin compositions of the examples and the comparative examples were measured.
The measurement results are shown in Table 2.

4.3 Evaluation of 5% thermogravimetric decrease temperature 5% thermogravimetric decrease temperature was measured for the cured film of the photosensitive resin composition of each example and each comparative example.
The measurement results are shown in Table 2.

4.4 Evaluation of Tensile Strength, Tensile Elastic Modulus, and Tensile Elongation Tensile strength, tensile elastic modulus, and tensile elongation were measured for the cured films of the photosensitive resin compositions of Examples and Comparative Examples.
The measurement results are shown in Table 2.

4.5 Evaluation of chemical resistance Chemical resistance was measured for the cured films of the photosensitive resin compositions of Examples and Comparative Examples.
In addition, the chemical | medical agent used for evaluation is as follows.

・ N-methylpyrrolidone (NMP)
・ Dimethyl sulfoxide (DMSO)
・ Propylene glycol monomethyl ether (PGME)
・ Propylene glycol monomethyl ether acetate (PGMEA)
-Tetramethylammonium hydroxide (TMAH) 2.38 mass% aqueous solution Evaluation result is shown in Table 2.

  As is clear from Table 2, the photosensitive resin compositions of the respective examples had good patterning properties. Moreover, since the crack etc. did not generate | occur | produce in the cured film of the photosensitive resin composition of each Example, it was recognized that it has a comparatively favorable film | membrane characteristic (mechanical strength).

  In addition, although the experiment which changed the ratio of the crosslinking agent in Example 1 and 2 to 25 mass parts and 35 mass parts was performed, the evaluation result was the tendency similar to Examples 1 and 2.

  Moreover, although the experiment which changed the ratio of the photo-acid generator (photosensitive agent) in Example 1 and 2 to 8 mass parts and 12 mass parts was conducted, the evaluation result was the tendency similar to Examples 1 and 2. .

DESCRIPTION OF SYMBOLS 10 Semiconductor device 20 Semiconductor chip 21 Electrode pad 22 Conductive wire 30 Die pad 40 Lead 50 Mold part 60 Adhesive layer 70 Protective film

Claims (8)

A phenolic hydroxyl group-containing resin having a structure represented by the following formula (1a).

[Wherein X is an organic group having 1 to 30 carbon atoms, Y is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R is independently a hydroxyl group, a halogen atom or a carboxyl group. Group, saturated or unsaturated alkyl group having 1 to 20 carbon atoms, alkyl ether group having 1 to 20 carbon atoms, saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, and fragrance having 6 to 20 carbon atoms It is a monovalent substituent selected from the group consisting of organic groups having a group structure, and the substituent may be bonded via an ester bond, an ether bond, an amide bond, or a carbonyl bond. Moreover, p is an integer of 0-3. ] The phenolic hydroxyl group-containing resin according to claim 1, which has a structure represented by the following formula (1b).

[Wherein X is an organic group having 1 to 30 carbon atoms, Y is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R is independently a hydroxyl group, a halogen atom or a carboxyl group. Group, saturated or unsaturated alkyl group having 1 to 20 carbon atoms, alkyl ether group having 1 to 20 carbon atoms, saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, and fragrance having 6 to 20 carbon atoms It is a monovalent substituent selected from the group consisting of organic groups having a group structure, and the substituent may be bonded via an ester bond, an ether bond, an amide bond, or a carbonyl bond. Moreover, p is an integer of 0-3. ]   X is any one of an alkyl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an alkyloxyalkyl group having 4 to 12 carbon atoms. Item 3. The phenolic hydroxyl group-containing resin according to Item 1 or 2.   The phenolic hydroxyl group-containing resin according to any one of claims 1 to 3, wherein X is any one of a hexyl group, a cyclohexyl group, a benzyl group, and a methoxyethyl group. The phenolic hydroxyl group-containing resin according to any one of claims 1 to 4,
A photosensitizer,
The photosensitive resin composition characterized by having. The phenolic hydroxyl group-containing resin according to any one of claims 1 to 4,
A crosslinking agent capable of crosslinking with the phenolic hydroxyl group-containing resin;
A photosensitizer,
The photosensitive resin composition characterized by having. A semiconductor substrate;
A coating layer provided on the surface of the semiconductor substrate and containing a cured product of the photosensitive resin composition according to claim 5 or 6,
A semiconductor device comprising:   An electronic apparatus comprising the semiconductor device according to claim 7.

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