KR20220041532A - Polyimide resin, positive-type photosensitive resin composition, insulating film and semiconductor device - Google Patents

Abstract

The present specification relates to a polyimide resin, a positive-type photosensitive resin composition, an insulating film, and a semiconductor device. The polyimide resin and the positive-type photosensitive resin composition have high heat resistance, excellent compatibility, and excellent mechanical properties and chemical resistance.

Description

POLYIMIDE RESIN, POSITIVE-TYPE PHOTOSENSITIVE RESIN COMPOSITION, INSULATING FILM AND SEMICONDUCTOR DEVICE}

The present specification relates to a polyimide resin, a positive photosensitive resin composition, an insulating film, and a semiconductor device.

With the market expansion and technological development of the semiconductor industry due to the 4th revolution, the demand for smaller semiconductors is increasing, and the demand for semiconductor stability in more extreme environments is also increasing. This is an area that requires improvement in technology in the semiconductor packaging field. A photoresist made of polyimide resin is attracting attention as a material that can solve many of them. In the case of packaging materials, unlike photoresists used in the production of other internal substrates, they remain after exposure and development to form a pattern, so excellent physical properties are required.

The function of forming a pattern by photosensitizing is a characteristic that a photoresist should naturally possess, which now requires a higher-resolution pattern, and requires the ability to make a finer pattern. In addition, since it is a packaging material, insulation properties, heat resistance properties, and physical properties that can protect the device from the external environment are required at a very high level.

However, in the case of polyimide resin, although the basic properties such as insulation and physical properties of the polymer are excellent, if it is improved with a photosensitive material with high resolution, the trade-off problem in which the existing properties are remarkably deteriorated Have.

Korean Patent Publication No. 10-2020-0058812

An object of the present specification is to provide a polyimide resin, a positive photosensitive resin composition, an insulating film, and a semiconductor device.

An exemplary embodiment of the present specification provides a polyimide resin represented by the following formula (1).

[Formula 1]

In Formula 1,

A1 means a divalent linking group or a tetravalent linking group,

A2 means a divalent linking group,

L2 and L3 are the same as or different from each other and each independently -O-; Or a substituted or unsubstituted alkylene group,

l2 and l3 are 2, L2 is the same as or different from each other, L3 is the same as or different from each other,

n is an integer from 1 to 90, and when n is 2 or more, the structures in parentheses are the same as or different from each other,

R3 and R4 are the same as or different from each other, and each independently hydrogen; hydroxyl group; Or a substituted or unsubstituted alkyl group,

r3 and r4 are the same as or different from each other, each independently an integer of 1 to 4, when r3 is 2 or more, R3 is the same as or different from each other, and when r4 is 2 or more, R4 is the same as or different from each other.

An exemplary embodiment of the present specification is a crosslinking agent comprising the polyimide resin; binder resin; photoactive compounds; Surfactants; And it provides a positive photosensitive resin composition comprising a solvent.

An exemplary embodiment of the present specification provides an insulating film including the positive photosensitive resin composition or a cured product thereof.

An exemplary embodiment of the present specification provides a semiconductor device including the insulating layer.

The polyimide resin according to the present specification and the positive photosensitive resin composition including the same have high heat resistance, excellent compatibility, and excellent mechanical properties and chemical resistance.

In the present specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.

In the present specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Hereinafter, the present specification will be described in more detail.

An exemplary embodiment of the present specification provides a polyimide resin including a structure represented by the following formula (1).

[Formula 1]

In Formula 1,

A1 means a divalent linking group or a tetravalent linking group,

A2 means a divalent linking group,

L2 and L3 are the same as or different from each other, and each independently -O-; Or a substituted or unsubstituted alkylene group,

l2 and l3 are 2, L2 is the same as or different from each other, L3 is the same as or different from each other,

n is an integer from 1 to 90, and when n is 2 or more, the structures in parentheses are the same as or different from each other,

R3 and R4 are the same as or different from each other, and each independently hydrogen; hydroxyl group; Or a substituted or unsubstituted alkyl group,

r3 and r4 are the same as or different from each other, each independently an integer of 1 to 4, when r3 is 2 or more, R3 is the same as or different from each other, and when r4 is 2 or more, R4 is the same as or different from each other.

The polyimide resin including the structure represented by Formula 1 according to an exemplary embodiment of the present specification serves as a crosslinking agent, and may be crosslinked by heat by including an epoxy group at the terminal, and the imide included in Formula 1 ( imide) structure may have low thermal properties and high mechanical properties.

In the case of a polyimide resin applied to a conventional photosensitive resin composition, a polyimide resin is used as a binder resin, but materials with low heat resistance and mechanical properties have been used for other crosslinking agents and additives. Accordingly, the excellent properties of the binder resin may be impaired. However, when the polyimide resin according to the present specification is applied to the positive photosensitive resin composition as a crosslinking agent, pixel resolution is increased and elongation characteristics are increased, thereby improving heat resistance and compatibility.

In particular, the polyimide resin including the structure represented by Chemical Formula 1 according to the present specification may obtain the above-described effect by including an epoxy group at the terminal thereof. Whether an epoxy group is included at the end of the polyimide resin can be confirmed by NMR measurement and FT-IR measurement. Specifically, multiple peaks were confirmed at 4.1 ppm to 4.2 ppm through NMR measurement, and the CO bond peak of the epoxy group at 960 cm ⁻¹ was confirmed through FT-IR measurement. You can see if it's included.

는 다른 치환기 또는 결합부에 결합되는 부위를 의미할 수 있고, 본 명세서의 중합체의 주쇄에 결합되는 부분을 의미할 수 있다. In this specification,

may mean a site bonded to another substituent or a bonding portion, and may mean a portion bonded to the main chain of the polymer of the present specification.

As used herein, the term "polymer" refers to a compound composed of repeating units (basic units). The polymer may be represented by a polymer or a compound made of a polymer.

In the present specification, examples of substituents are described below, but are not limited thereto.

In the present specification, the divalent linking group refers to a substituent having two bonding positions.

In the present specification, the tetravalent linking group refers to a substituent having four bonding positions.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; -COOH; alkoxy group; an alkyl group; cycloalkyl group; alkenyl group; cycloalkenyl group; aryl group; heteroaryl group; It means that it is substituted with one or more substituents selected from the group comprising a heterocyclic group containing one or more of N, O, S or P atoms or does not have any substituents.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkoxy group may be linear or branched, and the number of carbon atoms is not particularly limited, but may be 1 to 30, specifically 1 to 20, and more specifically 1 to 10.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 30. According to another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 10. Specific examples of the alkyl group include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-oxyl group tyl group and the like, but are not limited thereto. In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and particularly preferably a cyclopentyl group or a cyclohexyl group, but is not limited thereto. .

In the present specification, the alkylene group refers to a divalent alkyl group, and the above description may be applied to the alkyl group.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, there are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, but is not limited thereto.

In the present specification, the cycloalkylene group refers to a divalent cycloalkyl group, and the cycloalkyl group described above may be applied.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 30. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. Specific examples of the alkenyl group include, but are not limited to, an alkenyl group substituted with an aryl group such as a stylbenyl group or a styrenyl group.

In the present specification, the cycloalkenyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkenyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkenyl group is 3 to 20. According to another exemplary embodiment, the cycloalkenyl group has 3 to 6 carbon atoms. Examples of the cycloalkenyl group include, but are not limited to, a cyclopentenyl group and a cyclohexenyl group.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, an indenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

In the present specification, the arylene group refers to a divalent aryl group, and the above description may be applied to the aryl group.

In the present specification, the heterocyclic group is a heterocyclic group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but has 2 to 30 carbon atoms, specifically 2 to 20 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a triazine group, an acridyl group, a pyridazine group , quinolinyl group, isoquinoline group, indole group, carbazole group, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuran group and the like, but is not limited thereto.

In the present specification, the description of the above-described heterocyclic group may be applied, except that the heteroaryl group is aromatic.

In the present specification, the aromatic ring may be an aryl group or a heteroaryl group, the above-described description of the aryl group or heteroaryl group may be applied.

In the present specification, the aliphatic ring may mean a ring other than the aromatic ring.

In the present specification, as long as A1 is a divalent linking group or a tetravalent linking group, it may be employed without limitation.

In the present specification, as long as A2 is a divalent linking group, it may be employed without limitation.

는 하기 화학식 A-1 내지 A-3 중 하나이다. In one embodiment of the present specification, the formula (1)

is one of the following formulas A-1 to A-3.

[Formula A-1]

[Formula A-2]

[Formula A-3]

In Formulas A-1 to A-3,

는 상기 화학식 1에 결합되는 부분을 의미하고,

means a moiety bonded to Formula 1,

L1' and L2' are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted alkylene group; -O-; or -COO-L'-OCO-,

L' is a substituted or unsubstituted alkylene group,

Ra1 to Ra4 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group,

ra1 to ra4 are the same as or different from each other, each independently an integer of 0 to 3, when ra1 is 2 or more, Ra1 is the same as or different from each other, when ra2 is 2 or more, Ra2 is the same as or different from each other, and ra3 is 2 or more when Ra3 is the same as or different from each other, and when ra4 is 2 or more, Ra4 is the same as or different from each other,

Cy means a substituted or unsubstituted aliphatic ring or aromatic ring.

는 상기 화학식 A-2로 표시된다. In an exemplary embodiment of the present specification, when A1 is a divalent linking group,

is represented by Formula A-2.

는 상기 화학식 A-1 또는 상기 화학식 A-3로 표시된다. In the exemplary embodiment of the present specification, when A1 is a tetravalent linking group,

is represented by Formula A-1 or Formula A-3.

는 상기 화학식 A-1이다. In one embodiment of the present specification, the formula (1)

is the above formula A-1.

In one embodiment of the present specification, L1' and L2' are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted C1-C30 alkylene group; -O-; or -COO-L'-OCO-.

In one embodiment of the present specification, L1' and L2' are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted C 1 to C 20 alkylene group; -O-; or -COO-L'-OCO-.

In one embodiment of the present specification, L1' and L2' are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted C 1 to C 10 alkylene group; -O-; or -COO-L'-OCO-.

In an exemplary embodiment of the present specification, L1' is -O-; or -COO-L'-OCO-.

In an exemplary embodiment of the present specification, L1' is -O-.

In an exemplary embodiment of the present specification, L1' is -COO-L'-OCO-.

In an exemplary embodiment of the present specification, L' is a substituted or unsubstituted C1-C30 alkylene group.

In an exemplary embodiment of the present specification, L' is a substituted or unsubstituted C1-C20 alkylene group.

In an exemplary embodiment of the present specification, L' is a substituted or unsubstituted C 1 to C 10 alkylene group.

In an exemplary embodiment of the present specification, L' is a substituted or unsubstituted ethylene group.

In an exemplary embodiment of the present specification, L' is an ethylene group.

In an exemplary embodiment of the present specification, Ra1 to Ra4 are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted C 1 to C 30 alkyl group.

In an exemplary embodiment of the present specification, Ra1 to Ra4 are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted C 1 to C 20 alkyl group.

In an exemplary embodiment of the present specification, Ra1 to Ra4 are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted C 1 to C 10 alkyl group.

In an exemplary embodiment of the present specification, Ra1 to Ra4 are hydrogen.

In an exemplary embodiment of the present specification, Ra1 and Ra2 are hydrogen.

In an exemplary embodiment of the present specification, Cy is a substituted or unsubstituted aliphatic ring having 4 to 30 carbon atoms or a substituted or unsubstituted aromatic ring having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, Cy is a substituted or unsubstituted C 4 to C 20 aliphatic ring or a substituted or unsubstituted C 6 to C 20 aromatic ring.

In an exemplary embodiment of the present specification, Cy is a substituted or unsubstituted C4 to C10 aliphatic ring or a substituted or unsubstituted C6 to C12 aromatic ring.

In an exemplary embodiment of the present specification, Cy is a substituted or unsubstituted cyclobutane ring; a substituted or unsubstituted cyclohexane ring; Or a substituted or unsubstituted benzene ring.

In an exemplary embodiment of the present specification, Cy is a cyclobutane ring; cyclohexane ring; or a benzene ring.

In an exemplary embodiment of the present specification, A2 is (La2)la2, La2 is a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; or a substituted or unsubstituted arylene group, la2 is an integer of 1 to 3, and when la2 is 2 or more, La2 is the same as or different from each other.

In an exemplary embodiment of the present specification, La2 is a substituted or unsubstituted C 1 to C 30 alkylene group; a substituted or unsubstituted C 3 to C 30 cycloalkylene group; or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, La2 is a substituted or unsubstituted C 1 to C 20 alkylene group; a substituted or unsubstituted C 3 to C 20 cycloalkylene group; or a substituted or unsubstituted C6-C20 arylene group.

In an exemplary embodiment of the present specification, La2 is a substituted or unsubstituted C 1 to C 10 alkylene group; a substituted or unsubstituted C 3 to C 10 cycloalkylene group; or a substituted or unsubstituted arylene group having 6 to 12 carbon atoms.

In an exemplary embodiment of the present specification, La2 is a substituted or unsubstituted methylene group; or a substituted or unsubstituted phenylene group.

In an exemplary embodiment of the present specification, La2 is a methylene group substituted with -CF ₃ ; or a phenylene group substituted with -OH.

In one embodiment of the present specification, La2 may have the following structure.

는 상기 화학식 1에 결합되는 부분을 의미한다. In the structure,

denotes a moiety bonded to Formula 1 above.

In one embodiment of the present specification, L2 and L3 are the same as or different from each other and each independently -O-; or a substituted or unsubstituted C 1 to C 30 alkylene group.

In one embodiment of the present specification, L2 and L3 are the same as or different from each other and each independently -O-; or a substituted or unsubstituted C 1 to C 20 alkylene group.

In one embodiment of the present specification, L2 and L3 are the same as or different from each other and each independently -O-; or a substituted or unsubstituted C 1 to C 10 alkylene group.

In an exemplary embodiment of the present specification, L2 and L3 are the same as or different from each other, and each independently -O-; or a substituted or unsubstituted methylene group.

In an exemplary embodiment of the present specification, L2 and L3 are the same as or different from each other, and each independently -O-; or a methylene group.

In an exemplary embodiment of the present specification, R3 and R4 are the same as or different from each other, and each independently hydrogen; hydroxyl group; or a substituted or unsubstituted C 1 to C 30 alkyl group.

In an exemplary embodiment of the present specification, R3 and R4 are the same as or different from each other, and each independently hydrogen; hydroxyl group; or a substituted or unsubstituted C 1 to C 20 alkyl group.

In an exemplary embodiment of the present specification, R3 and R4 are the same as or different from each other, and each independently hydrogen; hydroxyl group; or a substituted or unsubstituted C 1 to C 10 alkyl group.

In an exemplary embodiment of the present specification, R3 and R4 are hydrogen.

In the exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas, but is not limited thereto.

In the above formula, n, m1 and m2 are the same as or different from each other, and each independently an integer of 1 to 90.

In an exemplary embodiment of the present specification, m1+m2 is an integer of 2 to 90.

In an exemplary embodiment of the present specification, the weight average molecular weight of the polyimide resin is 1,000 g/mol to 50,000 g/mol.

When the weight average molecular weight of the polyimide resin satisfies the above-mentioned range, there is an effect of having high mechanical properties and excellent developability at the same time.

The weight average molecular weight is one of the average molecular weights for which molecular weight is not uniform and the molecular weight of a certain polymer material is used as a reference, and is a value obtained by averaging the molecular weights of component molecular species of a polymer compound having a molecular weight distribution by weight fraction.

The weight average molecular weight may be measured by a gel permeation chromatography (GPC) method.

An exemplary embodiment of the present specification is a crosslinking agent comprising the polyimide resin; binder resin; photoactive compounds; Surfactants; And it provides a positive photosensitive resin composition comprising a solvent.

In an exemplary embodiment of the present specification, the positive photosensitive resin composition may include 2 parts by weight to 20 parts by weight of a crosslinking agent including the polyimide resin based on 100 parts by weight of the positive photosensitive resin composition; 10 parts by weight to 40 parts by weight of the binder resin; 1 part by weight to 8 parts by weight of the photoactive compound; 0.1 part by weight to 1 part by weight of the surfactant; and 40 to 80 parts by weight of a solvent.

Preferably, the positive photosensitive resin composition comprises 2 to 8 parts by weight of a crosslinking agent including the polyimide resin, based on 100 parts by weight of the positive photosensitive resin composition; 20 to 30 parts by weight of the binder resin; 1 part by weight to 5 parts by weight of the photoactive compound; 0.1 parts by weight to 0.5 parts by weight of the surfactant; and 50 to 70 parts by weight of a solvent.

When each of the components is included in the positive photosensitive resin composition in the above-described weight part range, it is developed in an alkaline developer and may have high mechanical properties and heat resistance.

In the present specification, the “polyimide resin” of the “crosslinking agent comprising a polyimide resin” refers to a polyimide resin having a structure represented by Formula 1 according to the present specification, and is included in the positive photosensitive resin composition. The “binder resin” used herein is a polyimide resin applied in the art other than a polyimide resin including a structure represented by Formula 1 according to the present specification, and does not include an epoxy group.

A polyimide resin other than the polyimide resin having a structure represented by Formula 1 may be employed without limitation as long as it is applied in the art.

The photoactive compound may be specifically a quinonediazide compound. The quinonediazide compound may be, for example, TPA529, THA515 or PAC430 of Miwon Corporation, but is not limited thereto.

In the crosslinking agent including the polyimide resin, the crosslinking agent may further include a crosslinking agent in addition to the polyimide resin having the structure represented by Formula 1 above. The further included crosslinking agent is not particularly limited, and can be used without limitation as long as it is applied in the art. The crosslinking agent further included is, for example, 2-[[4-[2-[4-[1,1-bis[4-(oxiran-2-ylmethoxy)phenyl]ethyl]phenyl]propan-2-yl]phenoxy] methyl]oxirane, 4,4'-methylenebis(N,N-bis(oxiran-2-ylmethyl)aniline), YD-127, YD-128, YD-129, YDF-170, YDF-175 of Kukdo Chemical Co., Ltd. YDF-180, DIC's EXA-4850, etc. can be used.

The surfactant is a silicone-based surfactant or a fluorine-based surfactant, and specifically, the silicone-based surfactant is BYK-Chemie's BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307 , BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341v344, BYK-345v346, BYK-348, BYK -354, BYK-355, BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, etc. can be used. As a fluorine-based surfactant, DIC (DaiNippon Ink & Chemicals) F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446 , F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F -486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF , TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc. may be used, but is not limited thereto.

As the solvent, a compound known to enable formation of a photosensitive resin composition in the art to which the present invention pertains may be applied without particular limitation. As a non-limiting example, the solvent may be at least one compound selected from the group consisting of esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

The ester solvent is ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate , gamma-butyrolactone, epsilon-caprolactone, delta-valerolactone, alkyl oxyacetate (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-oxypropionic acid alkyl esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, 3-methoxypropionic acid) methyl, 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate ethyl, etc.), 2-oxypropionate alkyl esters (eg, 2-oxypropionate methyl, 2-oxypropionate ethyl, 2- Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-oxy- 2-methylpropionate and 2-oxy-2-methylpropionate ethyl (eg, 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

The ether solvent is diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, di Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol It may be lycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.

The ketone solvent may be methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, or the like.

The aromatic hydrocarbon solvent may be toluene, xylene, anisole, limonene, or the like.

The sulfoxide solvent may be dimethyl sulfoxide or the like.

An exemplary embodiment of the present specification provides an insulating film including a positive photosensitive resin composition or a cured product thereof.

The insulating layer may include the positive photosensitive resin composition as it is.

The insulating film may include a cured product of the positive photosensitive resin composition.

The light source for curing the photosensitive resin composition according to the present specification includes, for example, a mercury vapor arc emitting light having a wavelength of 250 nm to 450 nm, a carbon arc, an Xe arc, and the like, but is not necessarily limited thereto.

After curing the positive photosensitive resin composition, the insulating film may be further subjected to a heat treatment step if necessary.

The heat treatment may be performed by a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, and may be performed at a temperature of 180°C to 250°C, or 190°C to 220°C.

The insulating film exhibits excellent chemical resistance and mechanical properties, and thus may be preferably applied to an insulating film of a semiconductor device, an interlayer insulating film for a redistribution layer, and the like. In addition, the insulation may be applied to a photoresist, an etching resist, a solder top resist, or the like.

The insulating layer may include a support or a substrate.

The support or substrate is not particularly limited, and those known in the art may be used. For example, the board|substrate for electronic components, the thing in which the predetermined|prescribed wiring pattern was formed, etc. can be illustrated. Examples of the substrate include a metal substrate such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, aluminum, gold, nickel, or a glass substrate. As a material of the wiring pattern, for example, copper, solder, chromium, aluminum, nickel, gold, or the like may be used, but is not limited thereto. Preferably, the support or substrate may be a silicon wafer.

The coating method is not particularly limited, but a spray method, a roll coating method, a spin coating method, etc. may be used, and in general, a spin coating method is widely used. In addition, after forming the coating film, in some cases, the residual solvent may be partially removed under reduced pressure.

In the present specification, the thickness of the insulating layer may be 1㎛ to 100㎛. When the thickness range of the insulating film is satisfied, an insulating film having excellent chemical resistance and mechanical properties as desired in the present specification can be obtained. The thickness of the insulating layer may be measured using a scanning electron microscope (SEM).

An exemplary embodiment of the present specification provides a semiconductor device including the insulating layer.

The semiconductor device may be manufactured by further including various components commonly used in the art in addition to the insulating film.

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art.

Examples and Comparative Examples

production example

Preparation of polyimide crosslinking agent X1 having a structure represented by Formula 1

Bis-APAF (2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane) (30g) and 170g of propylene glycol methyl ether acetate (PGMEA) were sequentially added to a 500mL round-bottom flask, and the temperature was raised to 120℃ and stirred. After complete dissolution, the flask was cooled to 80°C, ODPA (4,4-oxydiphthalic dianhydride) (35g) and 3AP (3-Aminophenol) (6.9g) were added, and then together with Toluene (20g) at 150°C stirred. After completely dissolving it, after cooling to 50 ℃, γ-VL (gamma valerolactone) (2.1g), TEA (triethylamine) (5.5g) was diluted in 3ml of propylene glycol methyl ether acetate (PGMEA) was added. The mixed solution was stirred at 175° C. for 16 hours, installed to remove water through a Dean-Stark distillation apparatus, and then refluxed for 3 hours. The solution was recovered after cooling to room temperature. The weight average molecular weight (Mw) of the recovered polymer was confirmed using gel permeation chromatography (GPC), and was 4,400 g/mol.

Epichlorohydrin (6g) and NaOH (sodium hydroxide) (2.7g) were added to the polymer resin solution and stirred at 40°C for 16 hours. After filtering the resulting precipitate with a paper filter, the filtrate was purified by precipitation in methanol after removing the remaining reactants with a rotary evaporator.

After the reaction, it was confirmed that multiple peaks were generated in the vicinity of 4.1 ppm to 4.2 ppm through NMR measurement, and the CO bond peak of the epoxy group at 960 cm ^-1 was confirmed through FT-IR measurement, confirming that the epoxy group was synthesized on the polyimide resin.

Preparation of polyimide crosslinking agent X2 having a structure represented by Formula 1

Bis-APAF (2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane) (30g) and 170g of propylene glycol methyl ether acetate (PGMEA) were sequentially added to a 500mL round-bottom flask, and the temperature was raised to 120℃ and stirred. After complete dissolution, the flask was cooled to 80° C., ODPA (4,4-oxydiphthalic dianhydride) (17.5 g) TMEG (Ethylene glycol bis (trimellitic anhydride)) (23 g) and 3AP (3-Aminophenol) (7.4 g) ), and stirred at 150° C. together with toluene (20 g). After complete dissolution, after cooling to 50 ℃, γ-VL (gamma valerolactone) (2.1g), TEA (triethylamine) (5.5g) was diluted in 3ml of propylene glycol methyl ether acetate (PGMEA) was added. The mixed solution was stirred at 175° C. for 16 hours, and then installed to remove water through a Dean-Stark distillation apparatus, and then refluxed for 3 hours. The solution was recovered after cooling to room temperature. The recovered polymer had a weight average molecular weight (Mw) of 4,500 g/mol using gel permeation chromatography (GPC).

Epichlorohydrin (6.5g) and NaOH (sodium hydroxide) (3g) were added to the prepared polymer resin solution and stirred at 40°C for 16 hours. After filtering the resulting precipitate with a paper filter, the filtrate is purified by precipitating it in methanol after removing the remaining reactants with a rotary evaporator. After the reaction, it was confirmed that multiple peaks were generated in the vicinity of 4.1 ppm to 4.2 ppm through NMR measurement, and the CO bond peak of the epoxy group at 960 cm ^-1 was confirmed through FT-IR measurement, and it was confirmed that the epoxy group was synthesized on the polyimide resin. .

Preparation of binder resin A

2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane, Poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol), bis(2-aminopropyl ether) and 4,4- A polyimide resin made from a combination of oxydiphthalic dianhydride was prepared.

Specifically, Bis-APAF (2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane) (20g) and Poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene) in a 500mL round-bottom flask glycol) (30 g), trimellitic anhydride (2.6 g), and propylene glycol methyl ether acetate (PGMEA) were sequentially added and 170 g of propylene glycol methyl ether acetate (PGMEA) was added thereto, and the temperature was raised to 120 ° C. 4,4-oxydiphthalic dianhydride) (25 g) was added, and the mixture was stirred at 150° C. together with Toluene (20 g). After completely dissolving it, after cooling to 50 ℃, γ-VL (gamma valerolactone) (2.1g), TEA (triethylamine) (5.5g) was diluted in 3ml of propylene glycol methyl ether acetate (PGMEA) was added. The mixed solution was stirred at 175° C. for 16 hours, installed to remove water through a Dean-Stark distillation apparatus, and then refluxed for 3 hours. The solution was recovered after cooling to room temperature. The recovered polymer had a weight average molecular weight (Mw) of 20,400 g/mol using gel permeation chromatography (GPC).

Experimental example

A positive photosensitive resin composition was prepared with the components shown in Table 1 below.

Specifically, based on 100 parts by weight of the positive photosensitive resin composition, a positive photosensitive resin composition was prepared by using parts by weight and the remainder of each component shown in Table 1 below as a solvent (propylene glycol methyl ether acetate).

The prepared positive photosensitive resin composition was cured under the following conditions and evaluated, and the results are shown in Table 1 below.

After spin coating, soft bake was performed, exposure was performed using an exposure machine, and development was performed with a developer (2.38 wt% TMAH sol.), followed by post bake.

Resist evaluation conditions: PrB 120℃/120s, PB 180℃/2hr, thickness 5㎛,

exposure : 300~900 mJ/㎠ i-line stepper,

development : 23℃ 2.38 wt% TMAH (Tetramethylammonium hydroxide) solution, Dipping, DI water rinse

[Chemical resistance] (After soaking in amine-based stripper for 15 minutes, thickness is measured by Alpha-step)

After immersing the prepared insulating film with a thickness of 5 μm in an amine-based stripper for 15 minutes, the thickness was measured by Alpha-step, and the evaluation was performed under the following conditions.

Maintain thickness (O): no change in thickness

Thickness change (△): increase or decrease the thickness

[Elongation] (UTM measurement after film production)

The elongation of the prepared insulating film having a thickness of 5 μm was measured with a UTM (Universal Testing Machine) at room temperature 5 cm/min at a speed condition, and the following conditions were evaluated.

◎: 40% or more

○: 20% or more and less than 40%

△: 0 or more and less than 20%

[Heat resistance] (TMA measurement after film production)

The prepared insulating film having a thickness of 5 μm was measured with a thermomechanical analyzer (TMA), and evaluated under the following conditions.

◎: less than 50%

○: 50% or more and less than 70%

△: 70% or more

A: Binder resin of Preparation Example A, B: TPA529 (Miwon Corporation), C: YDF-170 (Kukdo Chemical), D: EXA-4850 (DIC), E: BYK-307 (BYK-Chemie)

According to Table 1, Examples 1 to 5, compared to Comparative Examples 1 and 2, there is no change in the thickness of the insulating film before and after manufacturing, so it is excellent in chemical resistance, and it can be confirmed that the mechanical properties are excellent due to the high elongation. In addition, in the case of heat resistance, it can be confirmed that Examples 1 to 5 are higher than Comparative Examples 1 and 2.

From this, by applying a polyimide resin having a structure represented by Formula 1 including an epoxy group at the terminal thereof, it can be used as a polymer crosslinking agent instead of a crosslinking agent commonly used in the art, and Formula 1 It was confirmed that, due to the improved physical properties of the polyimide resin including the structure represented by , it was possible to provide a positive photosensitive resin composition and an insulating film excellent in chemical resistance, mechanical properties, and heat resistance.

Claims (10)

A polyimide resin comprising a structure represented by the following formula (1):
[Formula 1]

In Formula 1,
A1 means a divalent linking group or a tetravalent linking group,
A2 means a divalent linking group,
L2 and L3 are the same as or different from each other, and each independently -O-; Or a substituted or unsubstituted alkylene group,
l2 and l3 are 2, L2 is the same as or different from each other, L3 is the same as or different from each other,
n is an integer from 1 to 90, and when n is 2 or more, the structures in parentheses are the same as or different from each other,
R3 and R4 are the same as or different from each other, and each independently hydrogen; hydroxyl group; Or a substituted or unsubstituted alkyl group,
r3 and r4 are the same as or different from each other, each independently an integer of 1 to 4, when r3 is 2 or more, R3 is the same as or different from each other, and when r4 is 2 or more, R4 is the same as or different from each other. The method according to claim 1, wherein the formula (1)

is a polyimide resin of one of the following formulas A-1 to A-3:
[Formula A-1]

[Formula A-2]

[Formula A-3]

In Formulas A-1 to A-3,

means a moiety bonded to Formula 1,
L1' and L2' are the same as or different from each other, and each independently a direct bond; a substituted or unsubstituted alkylene group; -O-; or -COO-L'-OCO-,
L' is a substituted or unsubstituted alkylene group,
Ra1 to Ra4 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group,
ra1 to ra4 are the same as or different from each other, each independently an integer of 0 to 3, when ra1 is 2 or more, Ra1 is the same as or different from each other, when ra2 is 2 or more, Ra2 is the same as or different from each other, and ra3 is 2 or more when Ra3 is the same as or different from each other, and when ra4 is 2 or more, Ra4 is the same as or different from each other,
Cy means a substituted or unsubstituted aliphatic ring or aromatic ring. The method according to claim 1, wherein A2 is (La2)la2,
La2 is a substituted or unsubstituted alkylene group; a substituted or unsubstituted cycloalkylene group; Or a substituted or unsubstituted arylene group,
la2 is an integer from 1 to 3,
When la2 is 2 or more, La2 is the same as or different from each other. The method according to claim 1, L2 and L3 are the same as or different from each other, each independently -O-; Or a polyimide resin that is a substituted or unsubstituted methylene group. The polyimide resin according to claim 2, wherein L' is a substituted or unsubstituted ethylene group. The method according to claim 3, La2 is a substituted or unsubstituted methylene group; Or a polyimide resin that is a substituted or unsubstituted phenylene group. A crosslinking agent comprising the polyimide resin according to any one of claims 1 to 6; binder resin; photoactive compounds; Surfactants; And a positive photosensitive resin composition comprising a solvent. The method according to claim 7, based on 100 parts by weight of the positive photosensitive resin composition
2 to 20 parts by weight of a crosslinking agent including the polyimide resin;
10 parts by weight to 40 parts by weight of the binder resin;
1 part by weight to 8 parts by weight of the photoactive compound;
0.1 part by weight to 1 part by weight of the surfactant; and
A positive photosensitive resin composition comprising 40 parts by weight to 80 parts by weight of a solvent. An insulating film comprising the positive photosensitive resin composition according to claim 7 or a cured product thereof. A semiconductor device comprising the insulating film according to claim 9 .