CN117751326A - Method for producing cured product, method for producing laminate, method for producing semiconductor device, resin composition, cured product, laminate, and semiconductor device - Google Patents

Method for producing cured product, method for producing laminate, method for producing semiconductor device, resin composition, cured product, laminate, and semiconductor device Download PDF

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Publication number
CN117751326A
CN117751326A CN202280053079.7A CN202280053079A CN117751326A CN 117751326 A CN117751326 A CN 117751326A CN 202280053079 A CN202280053079 A CN 202280053079A CN 117751326 A CN117751326 A CN 117751326A
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group
formula
cured product
producing
compound
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野崎敦靖
高岛美沙树
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a method for producing a cured product, a method for producing a laminate using the method for producing a cured product, and a method for producing a semiconductor device, wherein a resin composition and a cured product obtained by curing the resin composition, a laminate including the cured product, and a semiconductor device, each of which has less outgassing from the obtained cured product. The method for producing a cured product comprises a film formation step of applying a resin composition containing a precursor of a cyclized resin to a substrate to form a film, and a heating step of heating the film at a heating temperature of 180 ℃ or lower, wherein the glass transition temperature of the obtained cured product is 200 ℃ or higher.

Description

Method for producing cured product, method for producing laminate, method for producing semiconductor device, resin composition, cured product, laminate, and semiconductor device
Technical Field
The present invention relates to a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, a resin composition, a cured product, a laminate, and a semiconductor device.
Background
Cyclized resins such as polyimide are excellent in heat resistance, insulation properties, and the like, and therefore can be used for various applications. The application is not particularly limited, and examples of the application include use of a material or a protective film as an insulating film or a sealing material when a semiconductor device for actual mounting is taken as an example. Further, the film can be used as a base film, a cover film, or the like of a flexible substrate.
For example, in the above-mentioned applications, a cyclized resin such as polyimide is used in the form of a resin composition containing at least one of cyclized resins such as polyimide and precursors of cyclized resins.
Such a resin composition is applied to a substrate to form a photosensitive film by coating or the like, and then exposed to light, developed, heated or the like as necessary, whereby a cured product can be formed on the substrate.
The precursor of the cyclized resin such as a polyimide precursor is cyclized by heating, for example, to form a cyclized resin such as polyimide in a cured product.
The resin composition can be applied by a known coating method or the like, and therefore, it can be said that the resin composition is excellent in manufacturing suitability, for example, the shape, size, application position and the like of the applied resin composition are highly free in design and the like when applied. In addition to the high performance of the cyclized resin such as polyimide, the expansion of the application of the resin composition in industry is expected to be remarkable from the viewpoint of excellent suitability for such production.
For example, patent document 1 discloses a semiconductor device including a semiconductor wafer, a sealing material covering the semiconductor wafer, and a rewiring layer having an area larger than that of the semiconductor wafer in plan view, wherein an interlayer insulating film of the rewiring layer is heated to 700 ℃ at 10 ℃/min in an air atmosphere, and the weight reduction rate is 5 to 95% by weight.
Technical literature of the prior art
Patent literature
Patent document 1: japanese patent laid-open No. 2020-113748
Disclosure of Invention
Technical problem to be solved by the invention
In the method of obtaining a cured product by curing a resin composition containing a precursor of a cyclized resin, there is a case where less generation of outgas from the cured product is required.
The present invention provides a method for producing a cured product, which can produce a cured product with less outgas, a method for producing a laminate using the method for producing a cured product, and a method for producing a semiconductor device.
Further, the present invention aims to provide a resin composition which generates less outgas from the obtained cured product, a cured product obtained by curing the resin composition, a laminate comprising the cured product, and a semiconductor device.
Means for solving the technical problems
Examples of representative embodiments of the present invention are shown below.
<1> a method for producing a cured product, comprising:
a film forming step of forming a film by applying a resin composition containing a precursor of a cyclized resin to a substrate; and
A heating step of heating the film at a heating temperature of 180 ℃ or lower,
the glass transition temperature of the obtained cured product is 200 ℃ or higher.
<2> the method for producing a cured product according to <1>, wherein,
the heating temperature is 170 ℃ or lower.
<3> the method for producing a cured product according to <1> or <2>, wherein,
the film after the heating step is a polyimide film, and the imidization ratio of the film is 90% or more.
<4> the method for producing a cured product according to any one of <1> to <3>, further comprising an exposure step of selectively exposing the film between the film formation step and the heating step.
<5> the method for producing a cured product according to <4>, further comprising a developing step of developing the exposed film with a developer to form a pattern between the exposing step and the heating step.
<6> the method for producing a cured product according to <5>, wherein,
The developer contains an organic solvent.
<7> the method for producing a cured product according to <5> or <6>, wherein,
the developing step is a step of forming a negative pattern.
<8> the method for producing a cured product according to any one of <5> to <7>, wherein,
the developer contains a base.
<9> the method for producing a cured product according to any one of <5> to <8>, comprising a treatment step of bringing a treatment liquid containing a base into contact with the pattern between the development step and the heating step.
<10> the method for producing a cured product according to any one of <1> to <9>, wherein,
the above resin composition contains a sensitizer.
<11> the method for producing a cured product according to any one of <1> to <10>, wherein,
the resin composition contains a solvent, and the content of the precursor of the cyclized resin is 70 mass% or more relative to the total solid content of the resin composition.
<12> the method for producing a cured product according to any one of <1> to <11>, wherein,
the resin composition contains a polymerizable compound having a boiling point of 200 ℃ or higher at 1 atmosphere.
<13> the method for producing a cured product according to <12>, wherein,
the polymerizable compound having a boiling point of 200 ℃ or higher at 1 atmosphere is a compound having 3 or more (meth) acrylate groups.
<14> the method for producing a cured product according to any one of <1> to <13>, wherein,
the resin composition contains a polymerizable compound having an aliphatic ring structure.
<15> the method for producing a cured product according to any one of <1> to <14>, wherein,
the precursor of the cyclized resin is a resin having at least one of the repeating units represented by the following formula (2) and the repeating unit represented by the formula (PAI-2).
[ chemical formula 1]
In the formula (2), A 1 A is a 2 Each independently represents an oxygen atom or-NR z ，R 111 Represents a 2-valent organic group, R 115 Represents a 4-valent organic group, R 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group, R z Represents a hydrogen atom or a 1-valent organic group.
In the formula (PAI-2), R 117 Represents a 3-valent organic group, R 111 Represents a 2-valent organic group, A 2 Represents an oxygen atom or-NR z -，R 113 Represents a hydrogen atom or a 1-valent organic group, R z Represents a hydrogen atom or a 1-valent organic group.
<16> the method for producing a cured product according to <15>, wherein,
r in the above formula (2) 115 R in the formula (PAI-2) is a group represented by any one of the following formulas (X1-1) to (X1-3) or a group having an aliphatic ring structure of 1 or more 117 The compound is a group represented by any one of the following formulas (X2-1) to (X2-3) or a group having an aliphatic ring structure of 1 or more.
[ chemical formula 2]
In the formula (X1-1), R represents a substituent, n1 represents an integer of 0 to 2, each represents a bonding site with other structure,
in the formula (X1-2), R independently represents a substituent, m1 independently represents an integer of 0 to 3, each represents a bonding site with other structure,
in the formula (X1-3), R independently represents a substituent, m1 independently represents an integer of 0 to 2, and L 1 representation-CR C 2 -or-S (=o) 2 -or-O-, R C Represents a 1-valent organic group, each represents a bonding site to another structure,
in the formula (X2-1), R represents a substituent, n2 represents an integer of 0 to 2, each represents a bonding site with other structure,
in the formula (X2-2), R independently represents a substituent, m2 represents an integer of 0 to 3, m3 represents an integer of 0 to 4, each represents a bonding site with other structure,
in the formula (X2-3), R independently represents a substituent, m2 represents an integer of 0 to 2, m3 represents an integer of 0 to 3, L 2 representation-CR C 2 -、-S(＝O) 2 -or-O-, R C Represents a 1-valent organic group, and each represents a bonding site to another structure.
<17> the method for producing a cured product according to <15> or <16>, wherein,
r in the above formula (2) 111 R in the formula (PAI-2) is a group represented by any one of the following formulas (W1-1) to (W1-5) or a group having an aliphatic ring structure of 1 or more 111 The compound is a group represented by any one of the following formulas (W1-1) to (W1-3) or a group having an aliphatic ring structure of 1 or more.
[ chemical formula 3]
In the formula (W1-1), R represents a substituent, n1 represents an integer of 0 to 4, each represents a bonding site with other structure,
in the formula (W1-2), R independently represents a substituent, m4 independently represents an integer of 0 to 4, each represents a bonding site with other structure,
in the formula (W1-3), R independently represents a substituent, m4 independently represents an integer of 0 to 3, and L 3 representation-CR C 2 -or-S (=o) 2 -，R C Represents a 1-valent organic group, each represents a bonding site to another structure,
in the formula (W1-4), R independently represents a substituent, n3 represents an integer of 0 to 6, each represents a bonding site with other structure,
in the formula (W1-5), R independently represents a substituent, n4 independently represents an integer of 0 to 3, and X 1 X is X 2 Each independently represents an oxygen atom, -S (=O) 2 or-CR C 2 -，R C Each independently represents a hydrogen atom or a 1-valent organic group, and each represents a bonding site to another structure.
<18> the method for producing a cured product according to any one of <15> to <17>, which satisfies at least one of the following conditions 1 and 2.
Condition 1: the precursor of the cyclized resin comprises-A in the formula (2) 2 -R 113 -A 1 -R 114 At least one of them is a repeating unit of a group represented by the following formula (3-1),
condition 2: the precursor of the cyclized resin comprises-A in the above formula (PAI-2) 2 -R 113 A repeating unit which is a group represented by the following formula (3-1),
[ chemical formula 4]
In the formula (3-1), Z 1 Z is as follows 2 Each independently represents an organic group, Z 1 And Z is 2 May be bonded to form a ring structure, meaning a bond site with other structures.
<19> a method for producing a laminate, comprising repeating the method for producing a cured product according to any one of <1> to <18> a plurality of times.
<20> a method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to any one of <1> to <18>, or the method for manufacturing a laminate according to <19 >.
<21> a resin composition comprising a precursor of a cyclized resin,
when the glass transition temperature is measured under the following measurement condition 1, the glass transition temperature of at least 1 of 3 films having different thicknesses is 200 ℃ or higher,
measurement condition 1:
the above resin composition was coated on a silicon substrate in a thickness of 5 μm, 10 μm or 20 μm, dried at 100℃for 5 minutes, and then heated at 180℃for 2 hours to obtain a cured product, and the glass transition temperature of the above cured product cooled to 25℃was measured by a differential scanning calorimeter.
<22> a cured product obtained by curing the resin composition of <21 >.
<23> a laminate comprising 2 or more layers formed of a cured product obtained by curing a resin composition containing a precursor of a cyclized resin,
at least one of the layers formed of the cured product is a layer formed of the cured product of <22 >.
<24> a semiconductor device comprising the cured product of <22> or the laminate of <23 >.
Effects of the invention
According to the present invention, there are provided a method for producing a cured product, a method for producing a laminate using the method for producing a cured product, and a method for producing a semiconductor device, each of which can produce a cured product with less outgas.
Further, according to the present invention, there are provided a resin composition which generates less outgas from the obtained cured product, a cured product obtained by curing the resin composition, a laminate comprising the cured product, and a semiconductor device.
Detailed Description
Hereinafter, a main embodiment of the present invention will be described. However, the present invention is not limited to the illustrated embodiments.
In the present specification, the numerical range indicated by the symbol "to" refers to a range in which numerical values before and after "to" are included as a lower limit value and an upper limit value, respectively.
In the present specification, the term "process" means not only an independent process but also a process which cannot be clearly distinguished from other processes as long as the intended function of the process can be achieved.
In the labeling of groups (atomic groups) in the present specification, the label which is not labeled with a substituted or unsubstituted group includes a group (atomic group) having no substituent, and includes a group (atomic group) having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, unless otherwise specified, "exposure" includes not only exposure by light but also exposure by a particle beam such as an electron beam or an ion beam. Examples of the light used for exposure include an open line spectrum of a mercury lamp, an active ray such as extreme ultraviolet rays (EUV light), X-rays, and electron beams, and radiation, which are typified by excimer laser light.
In the present specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", "(meth) acrylic" means either or both of "acrylic" and "methacrylic", and "(meth) acryl" means either or both of "acryl" and "methacryl".
In the present specification, me in the structural formula represents methyl, et represents ethyl, bu represents butyl, and Ph represents phenyl.
In the present specification, the total solid content refers to the total mass of the components other than the solvent among all the components of the composition. In the present specification, the solid content concentration is the mass percentage of the other components than the solvent with respect to the total mass of the composition.
In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by Gel Permeation Chromatography (GPC) and are defined as polystyrene equivalent values. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using, for example, HLC-8220GPC (manufactured by TOSOH CORPORATTON) in series with a protection column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATI0N, above) as a column. These molecular weights were measured using THF (tetrahydrofuran) as an eluent, unless otherwise specified. Among them, NMP (N-methyl-2-pyrrolidone) can be used when THF is not suitable as an eluent, for example, when solubility is low. Further, unless otherwise specified, a UV ray (ultraviolet ray) detector having a wavelength of 254nm is used for detection in GPC measurement.
In the present specification, when the positional relationship of each layer forming the laminate is described as "up" or "down", it is sufficient that another layer exists above or below the layer serving as the reference among the layers concerned. That is, the 3 rd layer or the 3 rd element may be further interposed between the layer to be the reference and the other layer, and the layer to be the reference and the other layer do not need to be in contact. If not specifically described, the direction in which the base material layers are stacked is referred to as "up", or the direction from the base material toward the resin composition layer is referred to as "up", and the opposite direction is referred to as "down", when the resin composition layer is present. In addition, these vertical directions may be set for convenience in the present specification, and in a practical embodiment, the "upward" direction in the present specification may be oriented differently from the vertical direction.
In the present specification, unless otherwise specified, each component contained in the composition may contain 2 or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature was 23 ℃, the air pressure was 101, 325Pa (1 atm), and the relative humidity was 50% rh.
In the present specification, a combination of preferred embodiments is a more preferred embodiment.
(method for producing cured product)
The method for producing a cured product of the present invention comprises a film formation step of applying a resin composition containing a precursor of a cyclized resin to a substrate to form a film, and a heating step of heating the film at a heating temperature of 180 ℃ or lower, wherein the glass transition temperature of the obtained cured product is 200 ℃ or higher.
According to the method for producing a cured product of the present invention, a cured product with less outgas generation can be obtained.
The mechanism for obtaining the above effects is not clear, but is presumed as follows.
Conventionally, a resin composition containing a precursor of a cyclized resin has been used to obtain a cured product.
In the method for producing a cured product of the present invention, the heating temperature in the heating step is 180 ℃ or lower, and the glass transition temperature of the film after the heating step is 200 ℃ or higher.
Here, it is assumed that when the glass transition temperature is 200 ℃ or higher, the cyclizing rate of the cyclized resin in the film is high.
It is considered that the occurrence of outgas due to cyclization or the like occurring further in the film after curing can be suppressed because the cyclization rate at the time of curing at 180 ℃ or lower is high.
It is assumed that by these actions, the method for producing a cured product according to the present invention can suppress the amount of outgas generated even when the glass transition temperature of the cured product obtained by heating at a low temperature of 180 ℃ or lower is 200 ℃ or higher.
Further, when the resin composition contains a polymerizable compound, it is considered that the glass transition temperature is related to the structural rigidity and the reaction rate of the polymerizable compound. That is, it can be said that when the glass transition temperature is 200 ℃ or higher, the structure obtained by polymerizing the polymerizable compound is a relatively rigid structure, and the amount of unreacted polymerizable compound in the film is small.
It is considered that the structure obtained by polymerizing the polymerizable compound is a rigid structure, and thus the outgas is more easily suppressed from escaping.
Further, it is considered that since the amount of unreacted polymerizable compound is small, crosslinking becomes fine, and the escape of outgas is easily suppressed, and the generation of outgas due to the volatilization of the polymerizable compound itself is easily suppressed.
Further, it is considered that when the cyclization ratio is high, movement (migration) of metal ions from the metal layer to the cured product with the uncycled portion as a permeation path can be suppressed.
Therefore, it is presumed that the adhesion to metal is also improved when the glass transition temperature is 200 ℃ or higher.
Hereinafter, each step included in the method for producing a cured product of the present invention and physical properties of the cured product will be described in detail.
< film Forming Process >
The method for producing a cured product of the present invention includes a film formation step of applying a resin composition containing a precursor of a cyclized resin to a substrate to form a film.
The details of the resin composition will be described later.
[ substrate ]
The type of the substrate may be appropriately determined according to the application, and examples thereof include substrates for semiconductor production such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, metal substrates such as quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, ni, cu, cr, fe (for example, any of substrates formed of metal and substrates formed with a metal layer by plating, vapor deposition, and the like), papers, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, electrode plates of Plasma Display Panels (PDP), and the like, without particular limitation. In the present invention, a substrate for semiconductor production is particularly preferable, and a silyl material, a Cu substrate, and a mold substrate are more preferable.
Further, the surface of these substrates may be provided with an adhesion layer, an oxide layer, or the like formed of Hexamethyldisilazane (HMDS), or the like.
The shape of the base material is not particularly limited, and may be circular or rectangular.
The size of the base material is, for example, 100 to 450mm, preferably 200 to 450mm in diameter in the case of a circular shape. In the case of rectangular shapes, the length of the short side is, for example, 100 to 1000mm, preferably 200 to 700mm.
As the base material, for example, a plate-like base material (substrate) is preferably used.
When a resin composition is applied to the surface of a resin layer (for example, a layer formed of a cured product) or the surface of a metal layer to form a film, the resin layer and the metal layer serve as a base material.
As a method for applying the resin composition to a substrate, coating is preferable.
Examples of the application method include dip coating, air knife coating, curtain coating, bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. The spin coating method, the slit coating method, the spray coating method, or the inkjet method is more preferable from the viewpoint of film thickness uniformity, and the spin coating method and the slit coating method are preferable from the viewpoint of film thickness uniformity and productivity. By adjusting the solid content concentration and the coating conditions of the resin composition according to the method, a film having a desired thickness can be obtained.
In addition, a coating method can be appropriately selected according to the shape of the substrate, and spin coating, spray coating, ink jet method, or the like is preferable in the case of a round substrate such as a wafer, and slit coating, spray coating, ink jet method, or the like is preferable in the case of a rectangular substrate. In the case of spin coating, for example, a spin speed of 500 to 3,500rpm can be applied for about 10 seconds to 3 minutes.
Further, a method of transferring a coating film formed by previously applying the above-described applying method to a temporary support onto a substrate can also be applied.
As the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of japanese patent application laid-open publication No. 2006-023696 or 0096 to 0108 of japanese patent application laid-open publication No. 2006-047592 can be preferably used in the present invention.
Further, a step of removing an excess film on the end portion of the base material may be performed. Examples of such a process include Edge Bead Rinse (EBR) and back surface rinse.
Furthermore, the following pre-wetting process may be employed: before the resin composition is applied to the substrate, various solvents are applied to the substrate to improve wettability of the substrate, and then the resin composition is applied.
< drying Process >
The film may be subjected to a step of drying the formed film (layer) after the film forming step (layer forming step) to remove the solvent.
That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
The drying step is preferably performed after the film formation step and before the exposure step.
The drying temperature of the film in the drying step is preferably 50 to 150 ℃, more preferably 70 to 130 ℃, and even more preferably 90 to 110 ℃. Further, drying may be performed by decompression. The drying time may be exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.
< heating Process >
The method for producing a cured product of the present invention includes a heating step of heating the film at a heating temperature of 180 ℃ or lower.
Here, the film in the heating step may be a film (pattern) after development in an exposure step and a development step described later, may be a film after exposure step but without development step described later, or may be a film formed by the film forming step (and optionally the drying step) without other steps.
In the method for producing a cured product of the present invention, the film temperature is preferably 180 ℃ or less in all steps including the heating step. According to the above aspect, thermal damage or the like of a material such as a base material can be suppressed.
In the method for producing a cured product of the present invention, the film temperature is preferably 180 ℃ or less in all steps including the heating step. According to the above aspect, thermal damage or the like of a material such as a base material can be suppressed.
In the heating step, the resin such as polyimide precursor is cyclized into the resin such as polyimide.
In the heating step, the unreacted crosslinkable groups in the specific resin or the crosslinking agent other than the specific resin, which will be described later, are crosslinked.
The heating temperature (maximum heating temperature) in the heating step is preferably 20 to 180 ℃, more preferably 150 to 180 ℃, and even more preferably 160 to 180 ℃.
Here, the film after the heating step is preferably a polyimide film. Specifically, the resin contained in the film after the heating step is preferably a resin having an imide ring structure in the repeating unit.
The heating step is preferably a step of promoting the cyclization reaction of the precursor of the cyclized resin by heating the film, and more preferably a step of promoting the cyclization reaction of the precursor of the cyclized resin in the film by the action of a base generated from a specific resin or a base generator described later, a base permeated from a developer, a base permeated from a rinse solution, or the like.
That is, before and after the heating step, it is preferable that the cyclized resin obtained from the precursor of the cyclized resin in the film after the heating step has an increased cyclized rate.
Specifically, when the cyclization ratio (%) of the precursor of the cyclized resin in the film before the heating step is set to be the cyclization ratio a and the cyclization ratio (%) of the cyclized resin obtained from the precursor of the cyclized resin in the film after the heating step is set to be the cyclization ratio B, the difference between the cyclization ratios represented by the following formulas is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. The upper limit of the cyclization ratio is not particularly limited and may be 100%.
Difference between cyclization ratios = cyclization ratio B-cyclization ratio a
The method for measuring the cyclization ratio of the film will be described later.
The heating in the heating step is preferably performed at a heating rate of 0.1 to 30 ℃/min from the temperature at the start of heating to the maximum heating temperature. The temperature rise rate is more preferably 0.5 to 20℃per minute, and still more preferably 2 to 10℃per minute. The temperature rise rate is set to 1 ℃/min or more, whereby excessive volatilization of the acid or solvent can be prevented while ensuring productivity, and the residual stress of the cured product can be relaxed by setting the temperature rise rate to 12 ℃/min or less.
In the case of an oven capable of rapid heating, the heating is preferably performed at a heating rate of 1 to 30 ℃/sec, more preferably 2 to 20 ℃/sec, still more preferably 3 to 10 ℃/sec, from the temperature at the start of heating to the highest heating temperature.
The temperature at the start of heating is preferably 20 to 150 ℃, more preferably 20 to 130 ℃, still more preferably 25 to 120 ℃. The temperature at the start of heating means the temperature at the start of the step of heating to the highest heating temperature. For example, when the resin composition is applied to a substrate and then dried, the temperature of the film (layer) after drying is preferably increased from a temperature lower than the boiling point of the solvent contained in the resin composition by 30 to 200 ℃.
The heating time (heating time at the highest heating temperature) is preferably 30 minutes to 5 hours, more preferably 1 hour to 3 hours.
The range of variation of the temperature (the difference between the maximum value and the minimum value of the temperature in the heating time at the highest temperature) when the highest heating temperature is maintained is preferably 0.1 to 20 ℃, more preferably 0.1 to 10 ℃, and even more preferably 0.1 to 3 ℃.
In particular, in forming the multilayer laminate, the heating temperature is preferably 30 ℃ or higher, more preferably 80 ℃ or higher, still more preferably 100 ℃ or higher, particularly preferably 120 ℃ or higher, and most preferably more than 150 ℃ from the viewpoint of interlayer adhesiveness.
The upper limit of the heating temperature is 180℃or less, preferably 170℃or less.
The method for producing a cured product may or may not include a step of heating at a heating temperature exceeding 180 ℃.
The heating may be performed in stages. As an example, the following procedure may be performed: heating from 25 ℃ to 120 ℃ at 3 ℃/min and holding at 120 ℃ for 60 minutes, heating from 120 ℃ to 180 ℃ at 2 ℃/min and holding at 180 ℃ for 120 minutes. Further, it is also preferable to perform the treatment while irradiating ultraviolet rays as described in U.S. Pat. No. 9159547. Such a pretreatment step can improve the film characteristics. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in 2 stages or more, for example, the pretreatment in stage 1 may be performed at 100 to 150 ℃ and the pretreatment in stage 2 may be performed at 150 to 180 ℃.
Further, the cooling may be performed after the heating, and the cooling rate at this time is preferably 1 to 5 ℃/min.
The heating step is preferably performed in an atmosphere of low oxygen concentration by, for example, flowing an inert gas such as nitrogen, helium, or argon under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50ppm (volume ratio) or less, more preferably 20ppm (volume ratio) or less.
The heating in the heating step may be performed under normal pressure or under reduced pressure. When heating is performed under reduced pressure, the reduced pressure may be ended before the start of heating, the reduced pressure may be ended during the temperature rise after the start of heating, or the reduced pressure may be ended after the highest heating temperature is reached, and the point in time when the reduced pressure is ended is not particularly limited. The end of the depressurization means that the pressure becomes 20mmHg (volume ratio) or less. The pressure can be measured by a differential pressure gauge. Here, it is also preferable that the film is always under reduced pressure for a period of time when the maximum heating temperature is maintained.
The heating method in the heating step is not particularly limited, and examples thereof include a heating plate, an infrared oven, an electrothermal oven, a hot air oven, an infrared oven, and the like.
< Exposure procedure >
The film may be subjected to an exposure step of selectively exposing the film after the film forming step and before the heating step.
That is, the method for producing a cured product according to the present invention may include an exposure step of selectively exposing the film formed in the film forming step to light between the film forming step and the heating step.
Selective exposure refers to exposing a portion of the film. By performing selective exposure, an exposed region (exposed portion) and an unexposed region (non-exposed portion) are formed on the film.
The exposure amount is not particularly limited as long as the resin composition can be cured, and is preferably 50 to 10,000mJ/cm as calculated by the conversion of the exposure energy at 365nm 2 More preferably 200 to 8,000mJ/em 2 。
The exposure wavelength can be appropriately determined in the range of 190 to 1,000nm, preferably 240 to 550nm.
As the exposure wavelength, there may be mentioned (1) a semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) a metal halide lamp, (3) a high-pressure mercury lamp, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), broad wavelengths (g, h, 3 wavelengths of i-rays), (4) an excimer laser, a KrF excimer laser (wavelength 248 nm), an ArF excimer Laser (wavelength 193 nm), F 2 Excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic 532nm, third harmonic 355nm of YAG laser, etc. With respect to the resin composition, exposure based on a high-pressure mercury lamp is particularly preferable, and exposure based on i-rays is preferable. Thus, particularly high exposure sensitivity can be obtained.
The exposure method is not particularly limited as long as at least a part of the film formed of the resin composition is exposed, and examples thereof include exposure using a photomask, exposure by a laser direct imaging method, and the like.
< post-exposure heating Process >
The film may be subjected to a heating step (post-exposure heating step) after exposure.
That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.
It is also preferable that the cyclization ratio of the film after the heating step (i.e., the cyclization ratio of the cyclized resin obtained from the precursor of the cyclized resin) does not substantially increase before and after the post-exposure heating step.
Specifically, the difference between the cyclizing rates is 30% or less, more preferably 20% or less, and still more preferably 10% or less. The upper limit of the cyclization ratio is not particularly limited and may be 0%.
In particular, when the film does not contain a photobase generator described later, the difference in the cyclization ratio is preferably 30% or less, more preferably 20% or less, and still more preferably 10% or less. The upper limit of the cyclization ratio is not particularly limited and may be 0%.
The post-exposure heating step may be performed after the exposure step and before the development step.
The heating temperature in the post-exposure heating step is preferably 50 to 140 ℃, more preferably 60 to 120 ℃.
The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
The heating rate in the post-exposure heating step is preferably 1 to 12 ℃/min, more preferably 2 to 10 ℃/min, and even more preferably 3 to 10 ℃/min, from the temperature at the start of heating to the maximum heating temperature.
The temperature rise rate may be appropriately changed during the heating process.
The heating method in the post-exposure heating step is not particularly limited, and a known heating plate, oven, infrared heater, or the like can be used.
In addition, the heating is preferably performed in an atmosphere of low oxygen concentration by passing an inert gas such as nitrogen, helium, or argon.
< developing Process >
The exposed film may be subjected to a developing step of developing with a developer to form a pattern.
That is, the method for producing a cured product of the present invention may include a developing step of developing the film exposed in the exposing step with a developer to form a pattern. By performing development, one of the exposed portion and the non-exposed portion of the film is removed to form a pattern.
Here, the development in which the non-exposed portion of the film is removed by the development step is referred to as negative development, and the formed pattern is referred to as a negative pattern. Further, development in which the exposed portion of the film is removed by the developing step is referred to as positive development, and the formed pattern is referred to as a positive pattern.
In the present invention, the developing step is preferably a step of forming a negative pattern.
[ developer solution ]
As the developer used in the developing step, an aqueous alkali solution or a developer containing an organic solvent is mentioned, and a developer containing an organic solvent is preferable.
When the developer is an aqueous alkali solution, examples of the basic compound that can be contained in the aqueous alkali solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methylttripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethyl bis (2-hydroxyethyl) ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferably TMAH. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 0.3 to 3 mass% based on the total amount of the developer.
When the developer contains an organic solvent, examples of the esters include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, epsilon-caprolactone, delta-valerolactone, and alkyl alkoxyacetate (for example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate, and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), ethyl 2-alkoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol Monomethyl Ether (PGME), propylene glycol monomethyl ether acetate (PGMFA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like, and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, and the like, and as sulfoxides, dimethyl sulfoxide, and as alcohols, methanol, ethanol, isopropanol, diethylene glycol, methyl butanol, N-butyl glycol, methyl pyrrolidone, N-methyl pyrrolidone, and the like, and as methyl-pyrrolidone, and the like, and as alcohols, and as methyl-N-butyl amide, and the like, are preferable.
When the developer contains an organic solvent, 1 or 2 or more organic solvents can be used in combination. In the present invention, a developer containing at least 1 selected from cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferable, a developer containing at least 1 selected from cyclopentanone, γ -butyrolactone, and dimethyl sulfoxide is more preferable, and a developer containing cyclopentanone is most preferable.
When the developing solution contains an organic solvent, the content of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the developing solution. The content may be 100% by mass.
When the developer contains an organic solvent, the content of water is preferably 10 mass% or more, more preferably 5 mass% or more, further preferably 1 mass% or more, and particularly preferably 0.1 mass% or more, relative to the total mass of the developer. The content of the water is not particularly limited and may be 0% by mass.
It is also preferable that the developer contains at least 1 compound selected from the group consisting of bases and base generators.
According to the above aspect, it is considered that in the development step, the alkali or the alkali generator in the developer permeates into the film, and in the subsequent heating step, cyclization of the precursor of the cyclized resin is promoted by the action of the alkali generated from the alkali or the alkali generator.
As a result, it is considered that the cyclized resin obtained from the precursor of the cyclized resin in the film after the heating step has an increased cyclized rate, and even when heated at a low temperature of 180 ℃ or lower, the glass transition temperature increases, and the outgas generation is less.
In the above aspect, the developer preferably contains a base from the viewpoint of suppressing the amount of deaeration.
In the above aspect, the developer is preferably an organic solvent-containing developer.
Alkali-
The alkali is preferably an organic alkali from the viewpoint of reliability in the case of remaining in the cured product (adhesion to the substrate when the cured product is further heated).
The base is preferably an amino group-containing base, such as a primary amine, a secondary amine, a tertiary amine, an ammonium salt, and a tertiary amide, and in order to promote imidization, a primary amine, a secondary amine, and a tertiary amine are preferable, a secondary amine or a tertiary amine is more preferable, and a tertiary amine is most preferable.
The alkali is preferably an alkali which is less likely to remain in the cured product obtained from the viewpoint of mechanical properties (elongation at break) of the cured product, and is preferably an alkali whose residual amount is less likely to be reduced by volatilization, vaporization, or the like before heating from the viewpoint of promoting cyclization (imidization).
Therefore, the boiling point of the base is preferably 30℃to 350℃at normal pressure (101,325 Pa), more preferably 80℃to 270℃and still more preferably 100℃to 230 ℃.
Further, the boiling point of the base is preferably higher than the temperature obtained by subtracting 20 ℃ from the boiling point of the organic solvent contained in the developer, more preferably higher than the boiling point of the organic solvent contained in the developer.
For example, when the boiling point of the organic solvent is 100 ℃, the boiling point of the base used is preferably 80 ℃ or higher, and more preferably 100 ℃ or higher.
The pKa in DMSO (dimethyl sulfoxide) of the conjugate acid of the above base is preferably 1 or more, more preferably 3 or more. The upper limit of the pKa is not particularly limited, but is preferably 20 or less.
When the conjugate acid of the above base has a plurality of pKa in DMSO, at least 1 of them is preferably within the above range.
Here, the above pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid, and reference can be made to the values described in Determination of Organic Structures by Physical Methods (authors: brown, H.C., mcDaniel, D.H., haflinger, O., nachod, F.C.; braude, E.A., nachod, F.C.; academic Press, new York, 1955), data for Biochemical Research (authors: dawson, R.M.C. et al; oxford, clarendon Press, 1959). Regarding the compounds not described in these documents, the value calculated from the structural formula using software of ACD/pKa (manufactured by ACD/Labs) was used as the pKa.
Specific examples of the base contained in the developer include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, dimethylcyclohexylamine, aniline, N-methylaniline, N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1, 4-diazabicyclo [2.2.2] octane), N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, 1, 5-diaminopentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N, N-diethyl ethylenediamine, N, N, N ', N' -tetrabutyl-1, 6-hexamethylenediamine, spermine, diaminocyclohexyl, bis (2-methoxyethyl) amine, piperidine, methylpiperidine, piperazine, tropane (tropane), N-phenylbenzylamine, 1, 2-diphenylethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N, N-tetramethyl ethylenediamine, N, N-tetramethyl 1, 3-propanediamine, and the like.
When the developer contains an alkali, the content of the alkali is preferably 0.1 to 100% by mass, more preferably 0.3 to 30% by mass, and even more preferably 0.5 to 20% by mass, based on the total mass of the developer.
When the alkali is not liquid at 10 to 30 ℃, the content of the alkali is preferably 0.3 to 30% by mass, more preferably 0.5 to 20% by mass.
The alkali may be used alone or in combination of 1 kind or 2 or more kinds. When 2 or more kinds of alkali are used in combination in the developer, the total content of these is preferably within the above range.
Alkali generating agent
The developer may contain a base generator.
As the base generator, a photobase generator or a thermal base generator is exemplified, and a thermal base generator is preferable.
As the above-mentioned photobase generator or thermal base generator, for example, the base generator described as a component contained in the resin composition described later can be used without particular limitation.
When the developer contains the alkali generator, the content of the alkali generator is preferably 0.005 to 100% by mass, more preferably 0.05 to 20% by mass, and even more preferably 0.08 to 5% by mass based on the total mass of the developer.
The alkali generator may be used alone or in combination of 1 or more than 2. When 2 or more kinds of the alkali generators are used together in the developer, the total content of these is preferably within the above range.
The developer may further contain other components.
Examples of the other components include a known surfactant and a known defoaming agent.
[ method for supplying developer ]
The method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and there are the following methods: a method of immersing a substrate on which a film is formed in a developer, a spin-on immersion developing method of supplying a developer to a film formed on a substrate by a nozzle, or a method of continuously supplying a developer. The type of the nozzle is not particularly limited, and examples thereof include a direct current nozzle, a shower nozzle, a spray nozzle, and the like.
The method of supplying the developer by the direct-current nozzle or the method of continuously supplying the developer by the spray nozzle is preferable from the viewpoints of the permeability of the developer, the removability of the non-image portion, and the efficiency in production, and the method of supplying the developer by the spray nozzle is more preferable from the viewpoints of the permeability of the developer to the image portion.
The process of continuously supplying the developer to the substrate by the dc nozzle, then rotating the substrate to remove the developer from the substrate, after spin-drying, and then continuously supplying the developer again by the dc nozzle, and then rotating the substrate to remove the developer from the substrate may be employed, or the process may be repeated a plurality of times.
As a method for supplying the developer in the developing step, a step of continuously supplying the developer to the substrate, a step of holding the developer on the substrate in a substantially stationary state, a step of vibrating the developer on the substrate by ultrasonic waves or the like, a step of combining these, and the like can be used.
The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, and it is preferably 10 to 45 ℃, more preferably 18 to 30 ℃.
< treatment Process >
The method for producing a cured product of the present invention preferably includes a treatment step of bringing a treatment liquid containing at least 1 compound selected from a group consisting of a base and a base generator into contact with the pattern between a development step and a heating step, and more preferably includes a treatment step of bringing a treatment liquid containing a base into contact with the pattern between a development step and a heating step.
According to such a mode, it is considered that at least 1 compound selected from the group consisting of a base and a base generating agent contained in the treatment liquid permeates into the developed pattern.
As a result, it is considered that the cyclized resin obtained from the precursor of the cyclized resin in the film after the heating step has an increased cyclized rate, and the glass transition temperature increases even when heated at a low temperature of 180 ℃ or lower, whereby a cured product with less outgas generation can be obtained.
The treatment step is preferably a rinsing step of rinsing the pattern with the treatment liquid.
The treatment liquid is preferably a rinse liquid.
Further, it is preferable that the treatment liquid is a rinse liquid and the treatment step is a rinse step of cleaning the pattern with the rinse liquid.
That is, the treatment step is preferably a rinsing step of rinsing the pattern (the pattern obtained in the development step) with a rinse solution containing at least 1 compound selected from the group consisting of alkali and alkali generating agents.
The treatment step may be performed, for example, after the "other washing step" described later.
[ treatment liquid ]
The water content is preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 2% by mass or less, relative to the total mass of the treatment liquid. The lower limit of the water content is not particularly limited and may be 0 mass%.
As the treatment liquid, for example, a solvent that is different from a solvent contained in the developer (for example, an organic solvent that is different from an organic solvent contained in the developer) and contains at least 1 compound selected from a base and a base generator can be used.
Alkali-
The preferred mode of the alkali contained in the treatment liquid is the same as that of the alkali contained in the developing liquid.
Among them, tertiary amines are preferable as the base contained in the treatment liquid.
The base contained in the treatment liquid is preferably a base that does not react easily with a solvent (for example, cyclopentanone) used in the treatment liquid.
When the treatment liquid contains an alkali, the content of the alkali is preferably 0.1 to 100% by mass, more preferably 0.3 to 30% by mass, and even more preferably 0.5 to 20% by mass, based on the total mass of the treatment liquid.
When the alkali is not liquid at 10 to 30 ℃, the content of the alkali is preferably 0.3 to 30% by mass, more preferably 0.5 to 20% by mass.
The alkali may be used alone or in combination of 1 kind or 2 or more kinds. When 2 or more kinds of alkali are used in combination in the treatment liquid, the total content of these is preferably within the above range.
Alkali generating agent
The treatment fluid may comprise a base generator.
As the base generator, a photobase generator or a thermal base generator is exemplified, and a thermal base generator is preferable.
As the above-mentioned photobase generator or thermal base generator, for example, the photobase generator or thermal base generator described as a component contained in the resin composition described later can be used without particular limitation.
When the treatment liquid contains the alkali generator, the content of the alkali generator is preferably 0.005 to 100% by mass, more preferably 0.05 to 20% by mass, and still more preferably 0.08 to 5% by mass, based on the total mass of the treatment liquid.
The alkali generator may be used alone or in combination of 1 or more than 2. When 2 or more kinds of the alkali generators are used in combination in the treatment liquid, the total content of these is preferably within the above range.
Examples of the organic solvent contained in the treatment liquid include esters, preferably include ethyl acetate, n-butyl acetate, pentyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, methyl 2-alkoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-alkoxymethyl 2-alkoxypropionate, ethyl 2-alkoxymethyl 2-ethoxypropionate, etc.), methyl 2-alkoxymethyl 2-ethoxypropionate, etc.), and the like (for example, methyl 2-alkoxymethyl 2-ethoxypropionate, ethyl 2-alkoxymethyl 2-ethoxypropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol Monomethyl Ether (PGME), propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like, and as cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, and the like, and as sulfoxides, dimethyl sulfoxide, and as alcohols, methanol, ethanol, isopropanol, diethylene glycol, methyl butanol, N-butyl glycol, methyl pyrrolidone, N-methyl pyrrolidone, and the like, and as methyl amides, and the like, and as ketones, and as preferred examples.
In addition, when the base (for example, an organic base) is a liquid in an environment where the treatment liquid is used, the base can be used as a solvent or a base.
When the treatment liquid contains an organic solvent, 1 or 2 or more organic solvents may be used in combination. In the present invention, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferable, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferable, and cyclohexanone and PGMEA are further preferable.
When the treatment liquid contains an organic solvent, it is preferable that 50 mass% or more of the organic solvent is used, more preferably 70 mass% or more of the organic solvent is used, and still more preferably 90 mass% or more of the organic solvent is used, based on the total mass of the treatment liquid. The treatment liquid may be an organic solvent in an amount of 100 mass%.
The treatment fluid may also contain other components.
Examples of the other components include a known surfactant and a known defoaming agent.
[ method for supplying treatment liquid ]
The method for supplying the processing liquid is not particularly limited as long as the processing liquid can be brought into contact with the pattern obtained in the developing step, and examples thereof include a method for supplying the processing liquid onto the pattern obtained in the developing step. The method of supplying the substrate is not particularly limited, and there are a method of immersing the substrate in the treatment liquid, a method of supplying the substrate by spin immersion (pump), a method of supplying the treatment liquid by spraying on the substrate, and a method of continuously supplying the treatment liquid on the substrate by a mechanism such as a direct-current nozzle.
From the viewpoints of permeability of the processing liquid to the image portion and efficiency in production, there are methods of supplying the processing liquid by using a shower nozzle, a direct-current nozzle, a spray nozzle, or the like, and a method of continuously supplying the processing liquid by using a nozzle is preferable, and from the viewpoints of permeability of the processing liquid to the image portion, a method of holding the processing liquid supplied by using a nozzle on the substrate is more preferable.
The above-described supply methods of the treatment liquid (for example, a combination of a spin-coating immersion-based supply and a shower-based supply, a spin-coating immersion-based supply and a direct-current nozzle-based supply) may be used in combination. For example, spin-on immersion supply has an effect that the film swells and the treatment liquid easily permeates. The treatment liquid may be used in combination with at least 1 of the methods. In the present invention, the following modes may be adopted: a treatment process using a treatment liquid (for example, a rinse liquid in another rinse process described below) containing no alkali and no alkali generating agent is performed after the treatment liquid is supplied onto the pattern (for example, after the rinse liquid is supplied onto the pattern and the pattern is cleaned in another rinse process described below). The preferred mode of the treatment liquid containing no alkali and no alkali generating agent is the same as that of the rinse liquid in the other rinse steps described later.
The method of supplying the treatment liquid containing no alkali and no alkali generating agent to the pattern in the above embodiment is not particularly limited, and examples thereof include supply by spin-coating immersion.
The method of supplying the processing liquid in the above embodiment to the pattern is not particularly limited, and examples thereof include supply by spraying, supply by a direct-current nozzle, and the like.
It is considered that, when the alkali-free treatment liquid is supplied by spin-coating immersion, at least 1 compound selected from the alkali and the alkali generating agent in the treatment liquid supplied after the pattern swells and easily permeates into the pattern, and thus the effect of improving the elongation at break and the like can be more easily obtained. In addition, when the treatment liquid is supplied through a shower, a direct-current nozzle, or the like, the removability (flushing property) of the development residues and the like may be excellent.
As a method for supplying the treatment liquid in the treatment step, a step of continuously supplying the treatment liquid to the substrate, a step of holding the treatment liquid on the substrate in a substantially stationary state, a step of vibrating the treatment liquid on the substrate by ultrasonic waves or the like, a step of combining these, and the like can be used.
Among them, the treatment step is preferably a step of supplying the treatment liquid to the developed pattern by spraying or continuously supplying the treatment liquid thereto.
Further, it is also preferable that the development in the development step is performed by spin-coating immersion development, and that at least 1 pass of the supply by spraying or the continuous supply by a direct-current nozzle or the like is performed in the supply of the treatment liquid in the treatment step. It is considered that, according to the above-described aspect, the pattern swells by spin-coating immersion development, and at least 1 compound selected from the group consisting of alkali and alkali generating agent in the treatment liquid easily penetrates into the pattern, whereby the effect of improving the elongation at break and the like can be more easily obtained.
The treatment time in the treatment step (that is, the time for which the treatment liquid is in contact with the pattern) is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the treatment liquid in the treatment step is not particularly limited, and is preferably 10 to 45 ℃, more preferably 18 to 30 ℃.
< other rinsing Process >
The method for producing a cured product of the present invention may include a rinsing step (hereinafter, also referred to as "other rinsing step") of rinsing the pattern (the pattern obtained by the developing step) with a rinsing liquid containing neither an alkali nor an alkali generator.
The method for producing a cured product of the present invention may include, for example, another rinsing step before the treatment step and after the development step. In the method for producing a cured product according to the present invention, when the treatment step is not included, another rinsing step may be included after the development step and before the heating step.
The rinse liquid used in the other rinse steps may be the same liquid as the treatment liquid except that the base and the base generator are not contained, and the preferable mode of each component contained in the rinse liquid is the same as the preferable mode of each component other than the base and the base generator contained in the treatment liquid.
The rinse liquid can be supplied to the pattern by the same method as the above-described treatment liquid.
< post-development exposure Process >
The pattern obtained by the development step (the pattern after the rinsing step in the case of performing the rinsing step) may be subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step.
That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
In the post-development exposure step, for example, a reaction of cyclizing a polyimide precursor or the like by the light-sensitive base generator, a reaction of releasing an acid-decomposable group by the light-sensitive base generator, or the like can be promoted.
In the post-development exposure step, at least a part of the pattern obtained in the development step may be exposed, and preferably all of the pattern is exposed.
The exposure amount in the post-development exposure step is preferably 50 to 20,000mJ/cm as calculated by the exposure energy conversion at a wavelength at which the photosensitive compound has sensitivity 2 More preferably 100 to 15,000mJ/cm 2 。
The post-development exposure step can be performed using, for example, the light source in the exposure step, and preferably using broadband light.
< Metal layer Forming Process >
The pattern obtained by the development step (preferably, at least one of the heating step and the post-development exposure step) may be subjected to a metal layer forming step of forming a metal layer on the pattern.
That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably, at least one of a heating step and a post-developing exposure step is performed).
The metal layer is not particularly limited, and conventional metal species can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, more preferably copper and aluminum, and still more preferably copper.
The method for forming the metal layer is not particularly limited, and a conventional method can be applied. For example, the methods described in Japanese patent application laid-open No. 2007-157879, japanese patent application laid-open No. 2001-521288, japanese patent application laid-open No. 2004-214501, japanese patent application laid-open No. 2004-101850, U.S. Pat. No. 7888181B2, and U.S. Pat. No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift off (lift off), electroplating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, a patterning method in which sputtering, photolithography, and etching are combined, and a patterning method in which photolithography and electroplating are combined can be cited. A preferable embodiment of the plating includes electrolytic plating using a copper sulfate plating solution or a copper cyanide plating solution.
The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, in terms of the thickest part.
< physical Properties of cured product >
[ glass transition temperature ]
In the method for producing a cured product of the present invention, the glass transition temperature of the obtained cured product is 200℃or higher, preferably 220℃or higher, and more preferably 250℃or higher.
The upper limit of the glass transition temperature is not particularly limited, but is preferably 350℃or lower.
The glass transition temperature was calculated by the method described in the examples.
[ cyclization Rate ]
In the method for producing a cured product of the present invention, the cyclized resin obtained from the precursor of the cyclized resin in the film after the heating step preferably has a cyclized rate of 90% or more, more preferably 95% or more, still more preferably 98% or more, and particularly preferably 99% or more.
In particular, the film after the heating step is a polyimide film, and the imidization ratio of the polyimide is preferably 90% or more, more preferably 95% or more, still more preferably 98% or more, and particularly preferably 99% or more.
The upper limit of the cyclization ratio is not particularly limited and may be 100%.
The above cyclization ratio was calculated by the following method.
When the precursor of the cyclized resin is a polyimide precursor or a polyamideimide precursor, the infrared absorption spectrum of the film after the heating step is measured to obtain 1377cm as an absorption peak derived from the imide structure -1 A nearby peak intensity P1. Next, the film after the heating step was heat-treated at 350℃for 1 hour, and then the infrared absorption spectrum was measured again to obtain 1377cm -1 A nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the cyclization ratio (imidization ratio) can be determined according to the following formula.
Imidization ratio (%) = (peak intensity P1/peak intensity P2) ×100
When the precursor of the cyclized resin is a polybenzoxazole precursor, the acyl group-derived film after the heating step is obtainedThe absorption peak of the amine structure is 1650cm -1 A nearby peak intensity Q1. Next, the film is used at 1490cm -1 The absorption intensity of the aromatic ring observed nearby was normalized. Next, the film after the heating step was heat-treated at 350℃for 1 hour, and then the infrared absorption spectrum was measured again to obtain 1650cm -1 The peak intensity Q2 in the vicinity was measured at 1490cm -1 The absorption intensity of the aromatic ring observed nearby was normalized. Using the normalized values of the obtained peak intensities Q1 and Q2, the cyclization ratio (oxazolization ratio) can be obtained according to the following formula.
Oxazolification rate (%) = (normalized value of peak intensity Q1/normalized value of peak intensity Q2) ×100
In addition, in the measurement of the above cyclization ratio (imidization ratio, oxazolization ratio), the composition was contained in 1377cm -1 Or 1377em -1 Or 1490cm -1 Or 1650cm -1 When a compound having an absorption at a wavelength (for example, phthalimide) is used, the peak intensity derived from the compound may be excluded as a background value (background).
[ shape, etc. ]
The form of the cured product of the resin composition is not particularly limited, and may be selected from films, rods, spheres, pellets, and the like according to the application. In the present invention, the cured product is preferably in the form of a film. The shape of the cured product can be selected by patterning the resin composition according to the use of the resin composition, such as forming a protective film on a wall surface, forming a through hole for conduction, adjusting impedance, electrostatic capacitance, or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film formed from the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage of the film before and after the heating step is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less. The shrinkage ratio is a percentage of a change in volume before and after the heating step, and can be calculated from the following formula.
Shrinkage [% ] =100- (volume after heating process +.volume before heating process) ×100
The elongation at break of the cured product is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The upper limit of the elongation at break is not particularly limited, and may be, for example, 200% or less. Elongation at break can be measured according to JIS (Japanese Industrial Standards: japanese Industrial Standard) K6251: 2017.
The Coefficient of Thermal Expansion (CTE) of the cured product is preferably 70ppm/K or less, more preferably 60ppm/K or less, and still more preferably 50ppm/K or less. The lower limit of the CTE is not particularly limited and may be Oppm/K.
< use >
Examples of the field to which the method for producing a cured product of the present invention or the cured product of the present invention can be applied include an insulating film for an electronic device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. In addition, there are a sealing film, a substrate material (a base film or a cover film of a flexible printed circuit board, an interlayer insulating film), a case where a pattern is formed on an insulating film for practical mounting such as the above-mentioned one by etching, and the like. For these uses, for example, reference can be made to Science & Technology co., ltd, "high functionalization of polyimide and application Technology of application", release of polyimide material base and development "11 th 2011", release of polyimide material base and application "NTS, 8 th 2010, etc., of the kaki ben yan min/prison, CMC technical library.
The method for producing a cured product of the present invention and the cured product of the present invention can also be used for producing a plate surface such as an offset plate surface or a screen plate surface, use of a molded part in etching, production of a protective paint and a dielectric layer in electronics, particularly microelectronics, and the like.
(resin composition)
The resin composition used in the method for producing a cured product of the present invention will be described below.
< specific resin >
The resin composition of the present invention contains a precursor of a cyclized resin (specific resin).
The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.
In the present invention, the main chain means a relatively longest bonding chain in a resin molecule.
Examples of the cyclized resin include polyimide, polybenzoxazole, and polyamideimide.
The precursor of the cyclized resin is a resin whose chemical structure is changed by an external stimulus to form a cyclized resin, preferably a resin whose chemical structure is changed by heat to form a cyclized resin, and more preferably a resin whose chemical structure is changed by a ring-closure reaction by heat generation to form a ring structure.
Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor.
That is, the resin composition of the present invention preferably contains at least 1 resin (specific resin) selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor and a polyamideimide precursor as the specific resin.
The resin composition of the present invention preferably contains a polyimide precursor as a specific resin.
The specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group.
When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described later, more preferably contains a radical polymerization initiator described later and contains a radical crosslinking agent described later. If necessary, a sensitizer to be described later may be further contained. For example, a negative photosensitive film is formed from such a resin composition of the present invention.
The specific resin may have a polar conversion group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator described later. For example, a positive photosensitive film or a negative photosensitive film as a chemically amplified film is formed from such a resin composition of the present invention.
Here, the precursor of the cyclized resin is preferably a resin having at least one of a repeating unit represented by the following formula (2) and a repeating unit represented by the formula (PAI-2).
In the above embodiment, R in the following formula (2) is preferable from the viewpoint of suppressing the occurrence of outgas from the cured product 115 Is a group represented by any one of the following formulas (X1-1) to (X1-3) or a group comprising 1 or more aliphatic ring structures, and R in the following formula (PAI-2) 117 The compound is a group represented by any one of the following formulas (X2-1) to (X2-3) or a group having an aliphatic ring structure of 1 or more. Hereinafter, such a mode will be described as mode a.
In embodiment a, R in the following formula (2) is preferable from the viewpoint of suppressing the occurrence of outgas from the cured product 111 Is a group represented by any one of the following formulas (W1-1) to (W1-5) or a group comprising 1 or more aliphatic ring structures, and R in the following formula (PAI-2) 111 The compound is a group represented by any one of the following formulas (W1-1) to (W1-5) or a group having an aliphatic ring structure of 1 or more.
Further, in the above embodiment a, at least one of the following conditions 1 and 2 is preferably satisfied in view of suppressing the occurrence of outgas from the cured product.
Condition 1: the precursor of the cyclized resin comprises-A in the formula (2) 2 -R 113 -A 1 -R 114 At least one of them is a repeating unit of a group represented by the following formula (3-1),
condition 2: the precursor of the cyclized resin comprises-A in the above formula (PAI-2) 2 -R 113 A repeating unit which is a group represented by the following formula (3-1),
more preferably as follows: the precursor of the cyclized resin satisfies the condition 1 when the repeating unit represented by the formula (PAI-2) is not contained, the precursor of the cyclized resin satisfies the condition 2 when the repeating unit represented by the formula (2) is not contained, and the precursor of the cyclized resin satisfies at least one of the conditions 1 and 2 when the repeating unit represented by the formula (2) and the repeating unit represented by the formula (PAI-2) are contained.
[ polyimide precursor ]
The polyimide precursor used in the present invention is not particularly limited in kind and the like, but preferably contains a repeating unit represented by the following formula (2).
[ chemical formula 5]
In the formula (2), A 1 A is a 2 Each independently represents an oxygen atom or-NR z -，R 111 Represents a 2-valent organic group, R 115 Represents a 4-valent organic group, R 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group, R z Represents a hydrogen atom or a 1-valent organic group.
A in formula (2) 1 A is a 2 Each independently represents an oxygen atom or-NR Z -, preferably an oxygen atom.
R z Represents a hydrogen atom or a 1-valent organic group, preferably a hydrogen atom. R is R z R represents a 1-valent organic group Z Is different from Z in the following formula (3-1) 1 The same is preferable.
R in formula (2) 111 Represents a 2-valent organic group. Examples of the 2-valent organic group include a group containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, preferably a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms. The hydrocarbon group in the chain of the above-mentioned straight chain or branched aliphatic group may be substituted with a heteroatom-containing group, and the cyclic hydrocarbon group of the above-mentioned cyclic aliphatic group and aromatic group may be substituted with a heteroatom-containing group. As a preferred embodiment of the present invention, examples thereof include-Ar-and-Ar-a group represented by L-Ar-and a group represented by L-Ar, particularly preferred are groups represented by-Ar-L-Ar-. Wherein Ar is an aromatic group, L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -or-NHCO-, or a group consisting of a combination of more than 2 of the above. The preferred ranges of these are as described above.
R 111 Preferably derived from diamines. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines. The diamine may be used in an amount of 1 or 2 or more.
Specifically, a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The hydrocarbon group in the chain of the above-mentioned straight chain or branched aliphatic group may be substituted with a heteroatom-containing group, and the cyclic hydrocarbon group of the above-mentioned cyclic aliphatic group and aromatic group may be substituted with a heteroatom-containing group. Examples of the group containing an aromatic group include the following groups.
[ chemical formula 6]
Wherein A represents a single bond or a 2-valent linking group, preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a fluorine atom, -O-, -C (=O) -, -S-, -SO 2 -, -NHCO-or combinations thereof, more preferably a single bond, selected from the group consisting of an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C (=O) -, -S-or-SO 2 The radicals in (E) -are further preferably-CH 2 -、-O-、-S-、-SO 2 -、-C(CF 3 ) 2 -or-C (CH) 3 ) 2 -。
Wherein, represents the bonding site with other structures.
Specific examples of the diamine include at least 1 diamine selected from the following: 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane and 1, 6-diaminohexane; 1, 2-or 1, 3-diaminocyclopentane, 1,2-, 1, 3-or 1, 4-diaminocyclohexane, 1,2, 1, 3-or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4 '-diamino-3, 3' -dimethylcyclohexylmethane, isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4' -and 3,3' -diaminobiphenyl, 4' -and 3, 3-diaminodiphenyl ether, 4' -or 3,3' -diaminodiphenylmethane, 4' -or 3,3' -diaminodiphenylsulfone 4,4' -or 3,3' -diaminodiphenyl sulfide, 4' -or 3,3' -diaminobenzophenone, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dimethoxy-4, 4' -diaminobiphenyl, and 2, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4' -diaminoterphenyl, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, bis [4- (2-aminophenoxy) phenyl ] sulfone, 1, 4-bis (4-aminophenoxy) benzene, 9, 10-bis (4-aminophenyl) anthracene, 3 '-dimethyl-4, 4' -diaminodiphenyl sulfone, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenyl) benzene, 3 '-diethyl-4, 4' -diaminodiphenyl methane 3,3 '-dimethyl-4, 4' -diaminodiphenylmethane, 4 '-diaminooctafluorobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) -10-hydroanthracene, 3',4,4 '-tetraminobiphenyl, 3',4 '-tetraminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3-dihydroxy-4, 4' -diaminobiphenyl, 9 '-bis (4-aminophenyl) fluorene, 4' -dimethyl-3, 3 '-diaminodiphenyl sulfone, 3',5 '-tetramethyl-4, 4' -diaminodiphenyl methane, 2, 4-and 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2,4, 6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzol, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecanefluoroheptane, 2-bis [4- (3-aminophenyl) hexafiuorophenoxy ] propane, 2-5-diaminophenoxy ] hexafluoropropane, 2, 4-bis [ 2, 3-aminophenyl ] hexafluoropropane For bis (4-amino-2-trifluoromethylphenoxy) benzene, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl 4,4' -bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4' -bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 3',5,5' -tetramethyl-4, 4' -diaminobiphenyl, 4' -diamino-2, 2' -bis (trifluoromethyl) biphenyl, 2', 5', 6' -hexafluoro-tolidine, and 4,4' -diaminotetrabiphenyl.
Further, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International publication No. 2017/038598 are also preferable.
Further, diamines having 2 or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of International publication No. 2017/038598 may be preferably used.
From the viewpoint of flexibility of the obtained organic film, R 111 Preferably represented by-Ar-L-Ar-. Wherein Ar is each independently an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -or-NHCO-, or a group consisting of a combination of more than 2 of the above. Ar is preferably a phenylene group which is preferably a phenylene group, L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom-O-, -CO-, -S-or-SO 2 -. Here, theThe aliphatic hydrocarbon group of (2) is preferably an alkylene group.
Moreover, from the viewpoint of the i-ray transmittance, R 111 The 2-valent organic group represented by the following formula (51) or (61) is preferable. In particular, from the viewpoints of i-ray transmittance and availability, the 2-valent organic group represented by formula (61) is more preferable.
(51)
[ chemical formula 7]
In the formula (51), R 50 ～R 57 Each independently is a hydrogen atom, a fluorine atom or a 1-valent organic group, R 50 ～R 57 At least 1 of which is a fluorine atom, a methyl group or a trifluoromethyl group, each independently represents a bonding site to a nitrogen atom in formula (2).
As R 50 ～R 57 Examples of the 1-valent organic group (1) include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).
[ chemical formula 8]
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In the formula (61), R 58 R is R 59 Each independently represents a fluorine atom, a methyl group or a trifluoromethyl group, and each independently represents a bonding site to a nitrogen atom in formula (2).
Examples of the diamine having the structure of formula (51) or (61) include 2,2 '-dimethylbenzidine, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, and 4,4' -diaminooctafluorobiphenyl. These may be used in 1 kind or in combination of 2 or more kinds.
In addition, R is also preferable from the viewpoint of suppressing the occurrence of outgas from the cured product 111 Is a group represented by any one of the following formulas (W1-1) to (W1-5)A group or a group comprising 1 or more aliphatic ring structures.
It is considered that by R 111 With such a structure, the glass transition temperature of the cured product increases, and the occurrence of outgas from the cured product can be suppressed.
[ chemical formula 9]
In the formula (W1-1), R represents a substituent, n1 represents an integer of 0 to 4, each represents a bonding site with other structure,
in the formula (W1-2), R independently represents a substituent, m4 independently represents an integer of 0 to 4, each represents a bonding site with other structure,
in the formula (W1-3), R independently represents a substituent, m4 independently represents an integer of 0 to 3, and L 3 representation-CR C 2 -or-S (=o) 2 -，R C Represents a 1-valent organic group, each represents a bonding site to another structure,
in the formula (W1-4), R independently represents a substituent, n3 represents an integer of 0 to 6, each represents a bonding site with other structure,
in the formula (W1-5), R independently represents a substituent, n4 independently represents an integer of 0 to 3, and X 1 X is X 2 Each independently represents an oxygen atom, -S (=O) 2 -or-CR C 2 -，R C Each independently represents a hydrogen atom or a 1-valent organic group, and each represents a bonding site to another structure.
In the present specification, when a bond is described as crossing an edge of a ring structure in a chemical formula, it means that the bond may be bonded to any ring-forming atom in the ring structure.
In the chemical formula, when a bond is described as spanning the edges of a plurality of ring structures, it means that the bond may be bonded to any ring-forming atom in the plurality of ring structures.
In the formula (W1-1), the substituent represented by R is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an aryl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an aryloxy group, an arylcarbonyl group, an aryloxycarbonyl group, an arylcarbonyloxy group, a halogen atom and the like.
The aliphatic hydrocarbon group is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.
The aryl group is preferably an aromatic hydrocarbon group, and more preferably a phenyl group.
The alkyl group in the above-mentioned alkoxy group, alkylcarbonyl group, alkoxycarbonyl group and alkylcarbonyloxy group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
The alkyl group may be further substituted with a halogen atom or the like. Examples of such a method include trifluoromethyl and pentafluoromethyl.
The aryl group in the aryloxy group, the arylcarbonyl group, the aryloxycarbonyl group, and the arylcarbonyloxy group is preferably an aromatic hydrocarbon group, and more preferably a phenyl group.
In the formula (W1-1), n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
In the formula (W1-2), R and m4 are preferably the same as R and n1 in the formula (W1-1), respectively.
In the formula (W1-3), the preferable mode of R is the same as that of R in the formula (W1-1).
In the formula (W1-3), m4 is preferably an integer of 0 to 2, more preferably 0 or 1.
In the formula (W1-3), L 3 representation-CR C 2 -or-S (=o) 2 -, preferably-S (=o) 2 -。
In the formula (W1-3), R C The preferred mode of (C) is the same as that of R in the formula (W1-1).
In the formula (W1-4), the preferable mode of R is the same as that of R in the formula (W1-1).
In the formula (W1-4), n3 is preferably an integer of 0 to 4, more preferably an integer of 0 to 2.
In the formula (W1-5), the preferable mode of R is the same as that of R in the formula (W1-1).
In the formula (W1-5), n4 is each independently preferably an integer of 0 to 2, more preferably 0 or 1.
In the formula (W1-5), X is preferable 1 X is X 2 One of them being an oxygen atom or-S (=o) 2 -, the other is-CR C 2 -。
In the formula (W1-5), R C Preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom.
Examples of the group containing 1 or more aliphatic ring structures include a group composed of 1 aliphatic ring structure or a group composed of 2 or more aliphatic ring structures bonded by a single bond, -O-, or-C (=o) -.
The aliphatic ring structure in the group containing 1 or more aliphatic ring structures may be a saturated aliphatic ring structure or an unsaturated aliphatic ring structure.
The aliphatic ring structure may be a heterocyclic structure, but is preferably an aliphatic hydrocarbon ring structure.
The aliphatic ring structure in the group containing 1 or more aliphatic ring structures may be a single ring or a heterocyclic ring such as a condensed ring, a crosslinked condensed ring, or a spiro ring.
Examples of the aliphatic ring structure in the group containing 1 or more aliphatic ring structures include a cyclohexane structure, a cyclohexene structure, and a bicyclo [2.2.2] oct-5-ene structure.
Specific examples of the group represented by any one of the formulae (W1-1) to (W1-5) or the group having an aliphatic ring structure of 1 or more include the following structures, but are not limited thereto. In the following structures, the bonding sites with other structures are indicated.
[ chemical formula 10]
R in formula (2) 115 Represents a 4-valent organic group. The 4-valent organic group is preferably a 4-valent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or (6).
In the formula (5) or (6), each independently represents a bonding site to another structure.
[ chemical formula 11]
In the formula (5), R 112 Is a single bond or a 2-valent linking group, preferably a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom-O-, -CO-, -S-, -SO 2 -and-NHCO-, and combinations thereof, more preferably a single bond, selected from the group consisting of alkylene groups having 1 to 3 carbon atoms which may be substituted with fluorine atoms, -O-, -CO-, -S-, and-SO 2 The radicals in are further preferably selected from the group consisting of-CH 2 -、-C(CF 3 ) 2 -、-C(CH 3 ) 2 -, -O-, -CO-; -S-and-SO 2 -a valence 2 group in (a).
Also, R is preferable from the viewpoint of suppressing the occurrence of outgas from the cured product 115 The compound is a group represented by any one of the following formulas (X1-1) to (X1-3) or a group having an aliphatic ring structure of 1 or more.
[ chemical formula 12]
In the formula (X1-1), R represents a substituent, n1 represents an integer of 0 to 2, each represents a bonding site with other structure,
in the formula (X1-2), R independently represents a substituent, m1 independently represents an integer of 0 to 3, each represents a bonding site with other structure,
in the formula (X1-3), R independently represents a substituent, m1 independently represents an integer of 0 to 3, and L 1 representation-CR C 2 -、-S(＝O) 2 -or-O-, R C Represents a 1-valent organic group, and each represents a bonding site to another structure.
In the formula (X1-1), the preferable mode of R is the same as that of R in the above formula (W1-1).
In the formula (X1-1), n1 is preferably 0 or 1.
In the formula (X1-2), the preferable mode of R is the same as that of R in the above formula (W1-1).
In the formula (X1-2), m1 is preferably 0 or 1.
In the formula (X1-3), the preferable mode of R is the same as that of R in the formula (W1-1).
In the formula (X1-3), m1 is preferably 0 or 1.
In the formula (X1-3), L 1 representation-CR C 2 -、-S(＝O) 2 -or-O-, preferably-S (=o) 2 -。
In the formula (X1-3), R C The preferred mode of (C) is the same as that of R in the formula (W1-1).
Preferred modes of the aliphatic ring structure in the group comprising 1 or more aliphatic ring structures are the same as those of R 111 The preferred mode of the aliphatic ring structure in the group comprising 1 or more aliphatic ring structures is the same.
Specific examples of the group represented by any one of the formulae (X1-1) to (X1-3) or the group having an aliphatic ring structure of 1 or more include the following structures, but are not limited thereto. In the following structures, the bonding sites with other structures are indicated.
[ chemical formula 13]
Specifically, R 115 The tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic dianhydride may be mentioned. As equivalent to R 115 The polyimide precursor may contain only 1 tetracarboxylic dianhydride residue or may contain 2 or more types.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
[ chemical formula 14]
In the formula (O), R 115 Represents a 4-valent organic group. R is R 115 Is preferably within the range of R in formula (2) 115 The meaning is the same, and the preferred ranges are also the same.
Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3',4' -biphenyl tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfide tetracarboxylic dianhydride, 3',4' -diphenyl sulfone tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfide tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfone tetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 4' -oxydiphthalic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,4,5, 7-naphthalene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalene tetracarboxylic dianhydride, 2',3,3' -diphenyltetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 1,2,4, 5-naphthalene tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 1,8,9, 10-phenanthrene tetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzene tetracarboxylic dianhydride, and alkyl groups having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.
As a preferable example, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International publication No. 2017/038598 can be mentioned.
In the formula (2), R may be 111 R is R 115 At least one of them having an OH group. More specifically, as R 111 The residue of a bisaminophenol derivative may be mentioned.
R in formula (2) 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group. As 1 priceAn organic group, preferably comprising a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkylene oxide group. Also, R is preferably 113 R is R 114 At least one of them comprises a polymerizable group, more preferably both comprise a polymerizable group. Also preferred is R 113 R is R 114 At least one of them contains 2 or more polymerizable groups. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, a radical, or the like, and is preferably a radical polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radical polymerizable group of the polyimide precursor is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group or the like), (meth) acrylamide group, (meth) acryloyloxy group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
[ chemical formula 15]
In the formula (III), R 200 Represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.
In formula (III), the bonding sites to other structures are represented.
In the formula (III), R 201 Represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -, cycloalkylene or polyalkoxyene groups.
R 201 Preferable examples of (C) include an alkylene group such as an ethenyl group, an propenyl group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, or a dodecamethylene group, a 1, 2-butanediyl group, a 1, 3-butanediyl group, and-CH 2 CH(OH)CH 2 -, polyalkoxylene, more preferably alkylene such as ethenyl or propenyl, -CH 2 CH(OH)CH 2 -, cyclohexyl, polyalkoxy, more preferably alkylene such as ethenyl, propenyl, or the like, or polyalkoxy.
In the present invention, the polyalkoxylene group means a group in which 2 or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkylene groups contained in the polyalkylene oxide groups may be the same or different, respectively.
When the polyalkylene oxide group contains a plurality of alkylene oxide groups having different alkylene groups, the alkylene oxide groups in the polyalkylene oxide group may be arranged randomly, may have a block or may have an alternating pattern.
The number of carbon atoms of the alkylene group (including the number of carbon atoms of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, still more preferably 2 to 6, still more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.
The alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and further preferably 2 to 6.
The polyalkylene oxide group is preferably a group in which a polyethylene oxide group, a polypropylene oxide group, a polytrimethylene group, a polytetramethylene group, or a plurality of ethylene oxide groups are bonded to a plurality of propylene oxide groups, more preferably a polyethylene oxide group or a polypropylene oxide group, and still more preferably a polyethylene oxide group, from the viewpoints of solvent solubility and solvent resistance. Among the groups in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, ethyleneoxy groups and propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern. Preferred modes of repeating the number of ethyleneoxy groups and the like in these groups are as described above.
In the formula (2), R is 113 In the case of hydrogen atoms or R 114 In the case of hydrogen atoms, the polymerizationThe imide precursor may form a conjugate salt with a tertiary amine compound having an ethylenically unsaturated bond. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
In the formula (2), R 113 R is R 114 At least one of them may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but is preferably an acetal group, a ketal group, a silyl ether group, a tertiary alkyl ester group or the like, and more preferably an acetal group or a ketal group from the viewpoint of exposure sensitivity.
Specific examples of the acid-decomposable group include a t-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a t-butoxycarbonylmethyl group, and a trimethylsilylether group. Ethoxyethyl or tetrahydrofuranyl is preferred from the viewpoint of exposure sensitivity.
In addition, from the viewpoint of suppressing the occurrence of outgas from the cured product, it is preferable to further contain-A 2 -R 113 -A 1 -R 114 At least one of them is a repeating unit of a group represented by the following formula (3-1).
[ chemical formula 16]
In the formula (3-1), Z 1 Z is as follows 2 Each independently represents an organic group, Z 1 And Z is 2 May be bonded to form a ring structure, meaning a bond site with other structures.
According to such a mode, it is considered that, when a specific resin is closed, a base is generated from the structure represented by the formula (3-1) and the closed loop is further promoted, and therefore, even a cured product obtained by heating at a low temperature of 180 ℃ or less increases in glass transition temperature, and a cured product with less outgas generation can be obtained.
In addition, for example, when a base generator described later is used, there is a case where a residue of the base generator after the generation of the base remains in the cured product, and this residue may be volatilized or the like to cause the generation of outgas. However, if the resin has a group represented by the formula (3-1), the residue is a closed-loop resin. Therefore, it is considered that the low molecular compound remains in the film after the heating step, and the amount of outgas generated is reduced.
When the specific resin has a group represented by the formula (3-1), the specific resin preferably generates a base at any temperature of 120 to 180 ℃.
The specific resin is preferably heated in the heating step to generate a base.
Whether a particular resin generates a base at a certain temperature X c can be judged by the following method.
After heating 1 mol of the specific resin in a closed vessel at 1 atmosphere at the above-mentioned X ℃ for 3 hours, the amount of decomposition was quantified by a method such as HPLC (high performance liquid chromatography), whereby it was possible to determine whether or not a base was generated. The amount of the base to be produced is preferably 0.1 mol or more, more preferably 0.5 mol or more. The upper limit of the amount of the base to be produced is not particularly limited, and can be set to 1000 moles or less, for example.
The molecular weight of the base produced from the specific resin is preferably 40 to 1,000, more preferably 40 to 500, and even more preferably 50 to 400.
The boiling point of the above-mentioned base having a pyridine structure at 1 atmosphere is preferably 50 to 600 ℃, more preferably 50 to 500 ℃, still more preferably 50 to 450 ℃.
The base to be produced is preferably a base having a pKa of 0 or more, more preferably 3 or more, and still more preferably 6 or more of the conjugate acid. The upper limit of the pKa of the conjugate acid is not particularly limited, but is preferably 30 or less.
pKa is a value that considers the dissociation reaction of hydrogen ions released by an acid and represents its equilibrium constant Ka by its negative common logarithmic pKa. In the present specification, unless otherwise specified, pKa is set to a calculated value based on ACD/ChemSketch (registered trademark).
When there are a plurality of pKa of the conjugate acid, it is preferable that at least 1 is within the above range.
In the formula (3-1), Z 1 Z is as follows 2 Each independently represents an organic group, preferably a hydrocarbon group or a hydrocarbon group and a group selected from-O-, -C (=O) -, -S (=O) 2 -and-NR N -a group represented by a combination of at least 1 group of the groups, preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and-0-. R is R N As described above.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group.
The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 8.
The aliphatic hydrocarbon group may have any one of a linear, branched, and cyclic structure, or may have a structure represented by a combination thereof.
The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 10, and still more preferably 6.
The above-mentioned hydrocarbon group may have a known substituent within a range where the effect of the present invention is obtained.
And Z is 1 Z is as follows 2 The mode in which at least 1 of them has a polymerizable group is also one of preferred modes of the present invention.
Examples of the polymerizable group include a radical polymerizable group, an epoxy group, an oxetanyl group, a hydroxymethyl group, and an alkoxymethyl group, and a radical polymerizable group is preferable.
The radical polymerizable group is preferably a group having an ethylenically unsaturated group, and examples thereof include a (meth) acryloyloxy group, a (meth) acrylamide group, a vinylphenyl group, a maleimide group, a styryl group, a vinyl group, and a (meth) allyl group.
Among them, (meth) acryloyloxy groups are preferable from the viewpoint of reactivity.
These polymerizable groups may be directly bonded to the nitrogen atom in the formula (3-1), or may be bonded via a linking group such as a hydrocarbon group (e.g., an alkylene group).
In the formula (3-1), Z 1 Z is as follows 2 May be bonded to form a ring structure.
The ring structure may be an aromatic ring structure or an aliphatic ring structure, and is preferably an aliphatic ring structure, and more preferably a saturated aliphatic ring structure.
The cyclic amine having 2 to 10 carbon atoms is preferable, and examples thereof include a pyrrolidine ring, a piperidine ring, a morpholine ring, an octahydroindole ring, an octahydroisoindole ring, a pyrrole ring, a pyridine ring, and the like, and a pyrrolidine ring, a piperidine ring, or a morpholine ring is preferable.
Further, the above-mentioned ring structure may have a substituent within a range where the effect of the present invention is obtained. Examples of the substituent include a hydrocarbon group and a halogen atom. Examples of the ring structure substituted with a substituent include a dimethylpiperidine ring.
The group represented by the formula (3-1) is preferably a group represented by the following formula (3-1-1) or by the formula (3-1-2).
[ chemical formula 17]
In the formula (3-1-1), cy represents an aliphatic ring structure or an aromatic ring structure, and represents a bonding site with other structure.
In the formula (3-1-2), Z 3 Z is as follows 4 Each independently represents an alkyl group, and represents a bonding site to another structure.
In the formula (3-1-1), the ring structure represented by Cy is preferably an aliphatic ring structure, more preferably a saturated aliphatic ring structure.
Examples of the ring structure represented by Cy include a pyrrolidine ring, a piperidine ring, a morpholine ring, an octahydroindole ring, an octahydroisoindole ring, a pyrrole ring, a pyridine ring, and the like, and a pyrrolidine ring, a piperidine ring, or a morpholine ring is preferable.
The ring structure represented by Cy may have a substituent within a range where the effect of the present invention is obtained. Examples of the substituent include a hydrocarbon group and a halogen atom. Examples of the ring structure substituted with a substituent include a dimethylpiperidine ring.
In the formula (3-1-2), Z 3 Z is as follows 4 Each independently represents an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 8 carbon atoms.
The alkyl group may have any of a linear, branched, and cyclic structure, or may have a structure represented by a combination thereof.
Specific examples of the group represented by the formula (3-1) include, but are not limited to, the following.
[ chemical formula 18]
The total molar amount of the groups represented by the formula (3-1) contained in the specific resin relative to-A in the formula (2) 2 -R 113 -A 1 -R 114 and-A in the following formula (PAI-2) 2 -R 113 The ratio of the total molar amount of (b) is preferably 0.1 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more.
In the above formula (2), -A 2 -R 113 -A 1 -R 114 and-A in the following formula (PAI-2) 2 -R 113 The total molar amount of the groups represented by the formula (3-1) can be calculated by NMR (nuclear magnetic resonance apparatus), for example.
Further, from the viewpoint of improving drug resistance and patterning properties, the total molar amount of the groups represented by the formula (3-1) relative to-A in the formula (2) 2 -R 113 -A 1 -R 114 and-A in the following formula (PAI-2) 2 -R 113 The ratio of the total molar amount of (c) is preferably 99.9 mol% or less, more preferably 95 mol% or less, further preferably 90 mol% or less, and particularly preferably 80 mol% or less.
Further, from the promotion of polyimide precursor resin and polyamideimide precursor The reason why the cyclization of the bulk resin reduces the heating temperature in the heating step and increases the elongation at break is considered that the molar amount of the group represented by the formula (3-1) contained in the specific resin relative to-A in the formula (2) 2 -R 113 -A 1 -R 114 and-A in the following formula (PAI-2) 2 -R 113 The ratio of the total molar amount of (c) is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably 98 mol% or more. The molar amount of the group represented by the formula (3-1) relative to-A in the formula (2) 2 -R 113 -A 1 -R 114 and-A in the following formula (PAI-2) 2 -R 113 The mode in which the proportion of the total molar amount of (a) is 100 mol% is also one of the preferred modes of the present invention.
The molar amount of the group represented by the formula (3-1) contained in the specific resin is preferably 0.001 to 10mmol/g, more preferably 0.01 to 5mmol/g, and even more preferably 0.1 to 3mmol/g, based on the total mass of the specific resin.
The content of the group represented by the formula (3-1) contained in the specific resin is preferably 0.1 to 70%, more preferably 0.5 to 40%, and even more preferably 1 to 20% based on the total mass of the specific resin.
Furthermore, the polyimide precursor preferably has a fluorine atom in the structure. The fluorine atom content in the polyimide precursor is preferably 10 mass% or more, and preferably 20 mass% or less.
In addition, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate. Specifically, as the diamine, bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like can be mentioned.
The repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (2-A). That is, at least 1 of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by the formula (2-a). The amplitude of the exposure latitude can be further increased by including the repeating unit represented by the formula (2-a) in the polyimide precursor.
(2-A)
[ chemical formula 19]
In the formula (2-A), A 1 A is a 2 Represents an oxygen atom, R 111 R is R 112 Each independently represents a 2-valent organic group, R 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group, R 113 R is R 114 At least one of them is a group containing a polymerizable group, and preferably both are groups containing a polymerizable group.
A 1 、A 2 、R 111 、R 113 R is R 114 Independently of A in formula (2) 1 、A 2 、R 111 、R 113 R is R 114 The meaning is the same, and the preferred ranges are also the same.
R 112 R in formula (5) 112 The meaning is the same, and the preferred ranges are also the same.
The polyimide precursor may contain 1 kind of repeating unit represented by the formula (2), or may contain 2 or more kinds. Further, a structural isomer of the repeating unit represented by formula (2) may be contained. Further, the polyimide precursor may obviously contain other kinds of repeating units than the repeating unit of the above formula (2).
As an embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by the formula (2) is 50 mol% or more based on the total repeating unit. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor other than the terminal may be the repeating unit represented by the formula (2).
The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 ～ 100,000, more preferably 10,000 ～ 50,000, and even more preferably 15,000 ～ 40,000. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000.
The molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.
In the present specification, the dispersity of the molecular weight is a value calculated by weight average molecular weight/number average molecular weight.
When the resin composition contains a plurality of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of at least 1 polyimide precursor be within the above-mentioned ranges. Further, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of polyimide precursors as 1 resin are each within the above-mentioned ranges.
[ polybenzoxazole precursor ]
The polybenzoxazole precursor used in the present invention is not particularly limited in its structure, and preferably contains a repeating unit represented by the following formula (3).
[ chemical formula 20]
In the formula (3), R 121 Represents a 2-valent organic group, R 12 w represents a 4-valent organic group, R 123 R is R 124 Each independently represents a hydrogen atom or a 1-valent organic group.
In the formula (3), R 123 R is R 124 Respectively with R in the formula (2) 113 The meaning is the same, and the preferred ranges are also the same. That is, at least one of them is preferably a polymerizable group.
In the formula (3), R 121 Represents a 2-valent organic group. The 2-valent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. As aliphaticA group, preferably a linear aliphatic group. R is R 121 Dicarboxylic acid residues are preferred. The dicarboxylic acid residues may be used in an amount of 1 or 2 or more.
The dicarboxylic acid residue is preferably an aliphatic group-containing dicarboxylic acid or an aromatic group-containing dicarboxylic acid residue, and more preferably an aromatic group-containing dicarboxylic acid residue.
As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferable, and a dicarboxylic acid composed of a linear or branched (preferably linear) aliphatic group and 2-COOH is more preferable. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, still more preferably 4 to 15, and particularly preferably 5 to 10. The straight chain aliphatic group is preferably an alkylene group.
As the dicarboxylic acid comprising a straight chain aliphatic group, examples thereof include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, and 2-methylglutaric acid, 3-methylglutaric acid, 2-dimethylglutaric acid, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoro-adipic acid, 3-methyladipic acid, pimelic acid, 2, 6-tetramethylpimelic acid, suberic acid, dodecafluoro-suberic acid, azelaic acid sebacic acid, hexadecanedioic acid, 1, 9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, ditridecanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, icosanedioic acid, triacontanedioic acid, tricosanedioic acid, diglycolic acid, dicarboxylic acids represented by the following formula, and the like.
[ chemical formula 21]
(wherein Z is a hydrocarbon group having 1 to 6 carbon atoms and n is an integer of 1 to 6.)
As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic group is preferable, and a dicarboxylic acid composed of only a group having the following aromatic group and 2-COOH is more preferable.
[ chemical formula 22]
Wherein A represents a member selected from the group consisting of-CH 2 -、-O-、-S-、-SO 2 -、-CO-、-NHCO-、-C(CF 3 ) 2 -and-C (CH) 3 ) 2 The 2-valent groups in (a) represent, independently of each other, bonding sites to other structures.
Specific examples of the dicarboxylic acid containing an aromatic group include 4,4 '-carbonyldibenzoic acid, 4' -dicarboxydiphenyl ether and terephthalic acid.
In the formula (3), R 122 Represents a 4-valent organic group. R in the above formula (2) is used as a 4-valent organic group 115 The meaning is the same, and the preferred ranges are also the same.
And R is 122 Preferably a group derived from a bisaminophenol derivative, as a group derived from a bisaminophenol derivative, for example, examples thereof include 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 4 '-diamino-3, 3' -dihydroxybiphenyl, 3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, 4 '-diamino-3, 3' -dihydroxydiphenyl sulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2-bis (3-amino-4-hydroxyphenyl) propane, and 2, 2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2-bis- (4-amino-3-hydroxyphenyl) propane, 4 '-diamino-3, 3' -dihydroxybenzophenone, 3 '-diamino-4, 4' -dihydroxydiphenyl Methanone, 4 '-diamino-3, 3' -dihydroxydiphenyl ether, 3 '-diamino-4, 4' -dihydroxydiphenyl ether, 1, 4-diamino-2, 5-dihydroxybenzene, 1, 3-diamino-2, 4-dihydroxybenzene, 1, 3-diamino-4, 6-dihydroxybenzene and the like. These bisaminophenols may be used alone or in combination.
Among the bisaminophenol derivatives, those having the following aromatic groups are preferable.
[ chemical formula 23]
Wherein X is 1 represents-O-, -S-, -C (CF) 3 ) 2 -、-CH 2 -、-S0 2 -, -NHCO-, and # each represent a bonding site to another structure. R represents a hydrogen atom or a 1-valent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group. And R is 122 The structure represented by the above formula is also preferable. R is R 122 In the case of the structure represented by the above formula, a total of 4 are preferably any 2 of them are R in the formula (3) 122 The bonding site of the bonded nitrogen atom and the other 2 are R in the formula (3) 122 The bonding site of the bonded oxygen atom is more preferably 2 x is R in formula (3) 122 The bonding site of the bonded oxygen atom and 2# are R in formula (3) 122 The bonding site or 2 of the bonded nitrogen atoms is R in formula (3) 122 The bonding site of the bonded nitrogen atom and 2 # are R in formula (3) 122 The bonding site of the bonded oxygen atom is more preferably 2 x is R in formula (3) 122 The bonding site of the bonded oxygen atom and 2# are R in formula (3) 122 Bonding sites for the bonded nitrogen atoms.
The bisaminophenol derivative is also preferably a compound represented by the formula (A-s).
[ chemical formula 24]
In the formula (A-s), R 1 Is selected from hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO 2 -, -CO-, -NHCO-; a single bond or an organic group in the following formula (A-sc). R is R 2 The hydrogen atom, alkyl group, alkoxy group, acyloxy group, and cyclic alkyl group may be the same or different. R is R 3 The hydrogen atom, linear or branched alkyl group, alkoxy group, acyloxy group, or cyclic alkyl group may be the same or different.
[ chemical formula 25]
(in the formula (A-sc): represents an aromatic ring bond with an aminophenol group of the bisaminophenol derivative represented by the formula (A-s))
It is considered that in the above formula (A-s), the amino group is located at the ortho position to the phenolic hydroxyl group, i.e., at R 3 The substituent is particularly preferable in that the distance between the carbonyl carbon of the amide bond and the hydroxyl group is further shortened and the effect of improving the cyclization ratio at the time of curing at low temperature is further improved.
In the above formula (A-s), R 2 Is alkyl and R 3 In the case of an alkyl group, the effect of high transparency to i-rays and high cyclization ratio when cured at low temperature can be maintained, and thus is preferable.
In the above formula (A-s), R is more preferably 1 Is an alkylene or substituted alkylene. As R 1 Specific examples of the alkylene group and substituted alkylene group include straight-chain or branched alkyl groups having 1 to 8 carbon atoms, and among them, from the viewpoint of maintaining the effect of high transparency to i-rays and high cyclization ratio at the time of curing at low temperature, and having sufficient solubility in a solvent and being capable of obtaining a polybenzoxazole precursor excellent in balance, more preferably-CH 2 -、-CH(CH 3 )-、-C(CH 3 ) 2 -。
Examples of the production method of the bisaminophenol derivative represented by the formula (A-s) include paragraphs 0085 to 0094 and example 1 (0189 to 0190) of Japanese unexamined patent publication No. 2013-256506, which are incorporated herein by reference.
Specific examples of the structure of the bisaminophenol derivative represented by the formula (A-s) include those described in paragraphs 0070 to 0080 of Japanese patent application laid-open No. 2013-256506, which are incorporated herein by reference. Of course, these are not limiting.
In addition to the repeating units of formula (3) above, the polybenzoxazole precursor may also contain other types of repeating units.
From the viewpoint of being able to suppress warpage accompanying closed-loop generation, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another kind of repeating unit.
[ chemical formula 26]
In the formula (SL), Z has a structure a and a structure b, R 1s Is hydrogen atom or hydrocarbon group with 1-10 carbon atoms, R 2s Is a hydrocarbon group of 1 to 10 carbon atoms, R 3s 、R 4s 、R 5s 、R 6s At least 1 of them is an aromatic group, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and may be the same or different. The polymerization of the a and b structures may be block polymerization or random polymerization. Regarding the mole% of the Z moiety, the a structure is 5 to 95 mole%, the b structure is 95 to 5 mole%, and a+b is 100 mole%.
In the formula (SL), preferable Z is R in the b structure 5s R is R 6s In the case of phenyl. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be reduced more effectively, and the effect of suppressing warpage and the effect of improving solvent solubility can be achieved at the same time.
IncludedWhen the diamine residue represented by the formula (SL) is used as another type of repeating unit, it is also preferable that the diamine residue further contains a tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic acid dianhydride as a repeating unit. Examples of such tetracarboxylic acid residues include R in formula (2) 115 Is an example of (a).
For example, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 ～ 30,000, more preferably 20,000 ～ 29,000, and further preferably 22,000 ～ 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The dispersion degree of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly limited, and is, for example, preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, still more preferably 2.3 or less, and still more preferably 2.2 or less.
When the resin composition contains a plurality of polybenzoxazole precursors as a specific resin, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity of at least 1 polybenzoxazole precursor are within the above-mentioned ranges. It is also preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated for the plurality of polybenzoxazole precursors as 1 resin are each within the above ranges.
[ Polyamide imide precursor ]
The polyamideimide precursor preferably contains a repeating unit represented by the following formula (PA-2).
[ chemical formula 27]
In the formula (PAI-2), R 117 Represents a 3-valent organic group, R 111 Represents a 2-valent organic group, A 2 Represents an oxygen atom or-NR z -，R 113 Represents a hydrogen atom or a 1-valent organic group, R z Represents a hydrogen atom or a valence of 1A machine group.
In the formula (PAI-2), R 117 Examples of the group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a group in which these groups are linked by a single bond or a linking group to 2 or more, preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a group in which these groups are combined by a single bond or a linking group to 2 or more, more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group to 2 or more.
As the above-mentioned linking group, a compound having a hydroxyl group, preferably-O-, -S-; -C (=o) -, -S (=o) 2 -, alkylene halide, arylene, or a linking group obtained by bonding 2 or more of these groups, more preferably-O-, -S-, alkylene halide, arylene, or a linking group obtained by bonding 2 or more of these.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and still more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, and may be substituted by a halogen atom, preferably all hydrogen atoms are substituted by halogen atoms. Examples of the preferred halogenated alkylene group include (bistrifluoromethyl) methylene.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1, 3-phenylene group or a 1, 4-phenylene group.
In addition, R is also preferable from the viewpoint of suppressing the occurrence of outgas from the cured product 117 Is any one of the following formulas (X2-1) to (X2-3)One represented group or a group having an aliphatic ring structure of 1 or more.
[ chemical formula 28]
In the formula (X2-1), R represents a substituent, n2 represents an integer of 0 to 2, each represents a bonding site with other structure,
In the formula (X2-2), R independently represents a substituent, m2 represents an integer of 0 to 3, m3 represents an integer of 0 to 4, each represents a bonding site with other structure,
in the formula (X2-3), R independently represents a substituent, m2 represents an integer of 0 to 2, m3 represents an integer of 0 to 3, L 2 representation-CR C 2 -、-S(＝O) 2 -or-O-, R C Represents a 1-valent organic group, and each represents a bonding site to another structure.
In the formula (X2-1), the preferable mode of R is the same as that of R in the above formula (W1-1).
In the formula (X2-1), n2 is preferably 0 or 1.
In the formula (X2-2), the preferable mode of R is the same as that of R in the above formula (W1-1).
In the formula (X2-2), m2 is preferably 0 or 1.
In the formula (X2-2), m3 is preferably 0 or 1.
In the formula (X2-3), the preferable mode of R is the same as that of R in the formula (W1-1).
In the formula (X2-3), m2 is preferably 0 or 1.
In the formula (X2-3), m3 is preferably 0 or 1.
In the formula (X2-3), L 2 representation-CR C 2 -、-S(＝O) 2 -or-O-, preferably-S (=o) 2 -。
In the formula (X2-3), R C The preferred mode of (C) is the same as that of R in the formula (W1-1).
Specific examples of the group represented by any one of the formulae (X2-1) to (X2-3) or the group having an aliphatic ring structure of 1 or more include the following structures, but are not limited thereto. In the following structures, the bonding sites with other structures are indicated.
[ chemical formula 29]
When the specific resin contains a group represented by any one of the formulae (X2-1) to (X2-3), the specific resin preferably contains the following structure.
[ chemical formula 30]
Preferred modes of the aliphatic ring structure in the group comprising 1 or more aliphatic ring structures are the same as those of R 111 The preferred mode of the aliphatic ring structure in the group comprising 1 or more aliphatic ring structures is the same.
And R is 117 Preferably from tricarboxylic acid compounds in which at least 1 carboxyl group can be halogenated. As the above halogenation, chlorination is preferable.
In the present invention, a compound having 3 carboxyl groups is referred to as a tricarboxylic acid compound.
2 carboxyl groups among 3 carboxyl groups of the above-mentioned tricarboxylic acid compound may be anhydrated.
Examples of the tricarboxylic acid compound which may be halogenated for producing the polyamideimide precursor include branched aliphatic, cyclic aliphatic, and aromatic tricarboxylic acid compounds.
Only 1 kind of these tricarboxylic acid compounds may be used, or 2 or more kinds may be used.
Specifically, as the tricarboxylic acid compound, a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining these groups by a single bond or a linking group of 2 or more, and more preferably, a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms or a group obtained by combining aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group of 2 or more.
Further, specific examples of the tricarboxylic acid compound include 1,2, 3-propane tricarboxylic acid, 1,3, 5-pentane tricarboxylic acid, citric acid, trimellitic acid, 2,3, 6-naphthalene tricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid by a single bond, -O-, -CH 2 -、-C(CH 3 ) 2 -、-C(CF 3 ) 2 -、-SO 2 Or a compound in which phenylene groups are bonded.
These compounds may be those obtained by anhydrating 2 carboxyl groups (for example, trimellitic anhydride), or those obtained by halogenating at least 1 carboxyl group (for example, trimellitic anhydride chloride).
In the formula (PAI-2), R 111 、A 2 、R 113 、R Z Respectively with R in the above formula (2) 111 、A 2 、R 113 、R Z The meaning is the same, and the preferred mode is the same.
The polyamideimide precursor may further comprise other repeating units.
Examples of the other repeating unit include a repeating unit represented by the above formula (2), a repeating unit represented by the following formula (PAI-1), and the like.
[ chemical formula 31]
In the formula (PAI-1), R 116 Represents a 2-valent organic group, R 111 Represents a 2-valent organic group.
In the formula (PAI-1), R 116 Examples of the aliphatic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, and a group in which these are linked by a single bond or a linking group to 2 or more, preferably a linear aliphatic group having 2 to 20 carbon atoms, a carbon atom number 3 to 20, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination of 2 or more of these groups by a single bond or a linking group, more preferably an aromatic group having 6 to 20 carbon atoms, or a combination of 2 or more of aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group.
As the above-mentioned linking group, a compound having a hydroxyl group, preferably-O-, -S-; -C (=o) -, -S (=o) 2 -, alkylene halide, arylene, or a linking group obtained by bonding 2 or more of these groups, more preferably-O-, -S-, alkylene halide, arylene, or a linking group obtained by bonding 2 or more of these.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and still more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, and may be substituted by a halogen atom, preferably all hydrogen atoms are substituted by halogen atoms. Examples of the preferred halogenated alkylene group include (bistrifluoromethyl) methylene.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1, 3-phenylene group or a 1, 4-phenylene group.
And R is 116 Preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
In the present invention, a compound having 2 carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having 2 halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide compound.
The carboxyl groups in the dicarboxylic acid dihalide compound may be halogenated, for example, preferably chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
Examples of the dicarboxylic acid compound or dicarboxylic acid dihalide compound which may be halogenated for producing the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compound or dicarboxylic acid dihalide compound, and the like.
These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used in an amount of 1 or 2 or more.
Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining 2 or more of these groups by a single bond or a linking group, and more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms or a group obtained by combining 2 or more of aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group.
Further, as a specific example of the dicarboxylic acid compound, examples thereof include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, and 2, 2-dimethylglutaric acid, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoro adipic acid, 3-methyladipic acid, pimelic acid, 2, 6-tetramethylpimelic acid, suberic acid, dodecafluoro suberic acid, azelaic acid, sebacic acid, hexadecyl sebacic acid, 1, 9-azelaic acid, dodecanedioic acid tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, icosanedioic acid, hencanedioic acid, docanedioic acid, ditridecanedioic acid, ditetradecanedioic acid, heptadecanedioic acid, octadecanedioic acid, icosanedioic acid, triacontanedioic acid, triamcinolone diacid, triacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4' -biphenylcarboxylic acid, 4' -dicarboxyl diphenyl ether, benzophenone-4, 4' -dicarboxylic acid, and the like.
Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure obtained by halogenating 2 carboxyl groups in the above specific examples of the dicarboxylic acid compound.
In the formula (PAI-1), R 111 R is the same as R in the above formula (2) 111 The meaning is the same, and the preferred mode is the same.
Furthermore, the polyamideimide precursor preferably also has a fluorine atom in the structure. The fluorine atom content in the polyamideimide precursor is preferably 10 mass% or more, and preferably 20 mass% or less.
In addition, the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to a substrate. Specifically, as the diamine component, there can be mentioned a method using bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, or the like.
One embodiment of the polyamideimide precursor in the present invention includes a repeating unit represented by the formula (PAI-2), a repeating unit represented by the formula (PAI-1), and a repeating unit represented by the formula (2) in a total amount of 50 mol% or more based on the total repeating units. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamideimide precursor other than the terminal may be any one of the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1) and the repeating unit represented by the formula (2).
In addition, another embodiment of the polyamideimide precursor in the present invention includes a structure in which the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyamideimide precursor other than the terminal may be any of the repeating units represented by the formula (PAI-2) or the repeating units represented by the formula (PAI-1).
The weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 ～ 500,000, more preferably 5,000 ～ 100,000, and even more preferably 10,000 ～ 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 25,000.
The molecular weight of the polyamideimide precursor has a dispersity of preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.0 or more. The upper limit of the molecular weight dispersivity of the polyamideimide precursor is not particularly limited, and is, for example, preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less.
When the resin composition contains a plurality of polyamide-imide precursors as the specific resin, it is preferable that the weight average molecular weight, the number average molecular weight, and the dispersity of at least 1 polyamide-imide precursor are within the above-mentioned ranges. Further, it is preferable that the weight average molecular weight, the number average molecular weight and the dispersity calculated as 1 resin of the plurality of polyamide-imide precursors are each within the above-mentioned ranges.
[ method for producing polyimide precursor and the like ]
The polyimide precursor and the like can be obtained, for example, by a method of reacting a tetracarboxylic dianhydride with a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at a low temperature to obtain a polyamic acid while esterifying the polyamic acid with a thickener or alkylating agent, a method of reacting a tetracarboxylic dianhydride with an alcohol in the presence of a diamine and a thickener after obtaining a diester with a tetracarboxylic dianhydride and an alcohol, a method of halogenating the remaining dicarboxylic acid with a halogenating agent after obtaining a diester with a tetracarboxylic dianhydride and an alcohol, and the like. Among the above production methods, more preferable is a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is halogenated with a halogenating agent and reacted with a diamine.
Examples of the thickener include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline, 1-carbonyldioxy-di-1, 2, 3-benzotriazole, N' -disuccinimide carbonate, and trifluoroacetic anhydride.
Examples of the alkylating agent include N, N-dimethylformamide dimethyl acetal, N-dimethylformamide diethyl acetal, N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate and the like.
Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphoryl chloride.
In the method for producing a polyimide precursor or the like, an organic solvent is preferably used in the reaction. The organic solvent may be 1 or 2 or more.
Examples of the organic solvent include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ -butyrolactone, which are appropriately determined according to the raw materials.
In the method for producing a polyimide precursor or the like, an alkali compound is preferably added at the time of the reaction. The number of the basic compounds may be 1 or 2 or more.
The basic compound can be appropriately determined depending on the starting materials, and triethylamine, diisopropylethylamine, pyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, N-dimethyl-4-aminopyridine, and the like can be exemplified.
Blocking agent-
In order to further improve the storage stability in the production of a polyimide precursor or the like, it is preferable to cap a carboxylic acid anhydride, an acid anhydride derivative, or an amino group remaining at the end of a resin such as a polyimide precursor. When the carboxylic acid anhydride and acid anhydride derivative remaining at the end of the resin are blocked, examples of the blocking agent include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like, and from the viewpoints of reactivity and film stability, monoalcohols, phenols, and monoamines are more preferably used. Preferred examples of the monoalcohol include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, tertiary alcohols such as t-butanol, adamantanol, and the like. Preferred examples of the phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Further, preferable examples of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminophenol, 3-aminophenol, thiophenol, and the like. These may be used in an amount of 2 or more, and various terminal groups may be introduced by reacting various kinds of blocking agents.
In addition, when the amino group at the end of the resin is blocked, a compound having a functional group reactive with the amino group can be used for blocking. Preferred capping agents for the amino group are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. Preferred examples of the carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2, 3-dicarboxylic anhydride. Preferred compounds of carboxylic acid chlorides include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearoyl chloride, benzoyl chloride, and the like.
Further, as the end-capping agent, a compound represented by the formula (T-1) may be used. It is considered that by blocking the terminal with such a compound, a structure that easily generates a base can be introduced into the terminal, and even if the resin is cured at a low temperature, the cyclizing rate of the cyclized resin obtained from the precursor of the cyclized resin is easily increased.
[ chemical formula 32]
In the formula (T-1), L T Represents a 2-valent organic group, Z 1 Z is as follows 2 Each independently represents an organic group, Z 1 And Z is 2 May be bonded to form a ring structure.
In the formula (T-1), L T The hydrocarbon group is preferably an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and preferably an aromatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group.
L T The link chain length (i.e., link and L) T The minimum number of atoms of the 2 carbonyl groups bonded) is preferably 2 to 4, more preferably 2.
In the formula (T-1), Z 1 Z is as follows 2 And Z in formula (3-1) 1 Z is as follows 2 The meaning is the same, and the preferred mode is the same.
In particular, Z 1 Z is as follows 2 The mode in which at least one of them has a polymerizable group is also one of preferred modes of the present invention.
Examples of the polymerizable group include a radical polymerizable group, an epoxy group, an oxetanyl group, a hydroxymethyl group, and an alkoxymethyl group, and a radical polymerizable group is preferable.
The radical polymerizable group is preferably a group having an ethylenically unsaturated group, and examples thereof include a (meth) acryloyloxy group, a (meth) acrylamide group, a vinylphenyl group, a maleimide group, a styryl group, a vinyl group, and a (meth) allyl group.
Among them, (meth) acryloyloxy groups are preferable from the viewpoint of reactivity.
These polymerizable groups may be directly bonded to the nitrogen atom in the formula (T-1), or may be bonded via a linking group such as a hydrocarbon group (e.g., an alkylene group).
Specific examples of the compound represented by the formula (T-1) include, but are not limited to, the following compounds.
[ chemical formula 33]
Solid precipitation-
The production of the polyimide precursor and the like may include a solid precipitation step. Specifically, the water-absorbing by-product of the dehydration thickener which is present in the reaction liquid is filtered as needed, and then the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol or a mixed liquid thereof, and the polymer component is precipitated, whereby the polymer component is precipitated as a solid and dried to obtain a polyimide precursor or the like. In order to improve the purification degree, operations such as redissolution, reprecipitation, precipitation, and drying may be repeated for the polyimide precursor or the like. The method may further comprise a step of removing ionic impurities using an ion exchange resin.
[ content ]
The content of the specific resin in the resin composition of the present invention is preferably 20 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, still more preferably 50 mass% or more, and particularly preferably 70 mass% or more, based on the total solid content of the resin composition.
Here, the resin composition of the present invention contains a solvent and the content of the precursor of the cyclized resin is 70 mass% or more relative to the total solid content of the resin composition, in terms of suppressing the generation amount of outgas, which is also one of preferred embodiments of the present invention.
The content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, still more preferably 98% by mass or less, still more preferably 97% by mass or less, and still more preferably 95% by mass or less, based on the total solid content of the resin composition.
The resin composition of the present invention may contain only 1 specific resin or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.
Furthermore, the resin composition of the present invention preferably further comprises at least 2 resins.
Specifically, the resin composition of the present invention may contain 2 or more types of specific resins and other resins described later in total, or may contain 2 or more types of specific resins, and preferably contains 2 or more types of specific resins.
When the resin composition of the present invention contains 2 or more specific resins, it is preferable that the resin composition contains a dianhydride-derived structure (R in the above formula (2)) 115 ) Different polyimide precursors of 2 or more types.
< other resins >
The resin composition of the present invention may contain the above specific resin and another resin (hereinafter, also simply referred to as "another resin") different from the specific resin.
Examples of the other resin include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth) acrylic resins, (meth) acrylamide resins, urethane resins, butyral resins, styrene resins, polyether resins, and polyester resins.
For example, by further adding a (meth) acrylic resin, a resin composition excellent in coatability can be obtained, and a pattern (cured product) excellent in solvent resistance can be obtained.
For example, the resin composition may be prepared by adding a resin having a weight average molecular weight of 20,000 or less and a high value of the polymerizable group (for example, 1X 10 in 1g of the resin having a molar amount of the polymerizable group) -3 Molar/g or more) of (meth) acrylic acid treeThe resin composition can be improved in coating property, solvent resistance of a pattern (cured product), and the like.
When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, further preferably 1 mass% or more, further preferably 2 mass% or more, further preferably 5 mass% or more, and further preferably 10 mass% or more, based on the total solid content of the resin composition.
The content of the other resin in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, still more preferably 70 mass% or less, still more preferably 60 mass% or less, and still more preferably 50 mass% or less, based on the total solid content of the resin composition.
In addition, as a preferred embodiment of the resin composition of the present invention, the content of other resins may be reduced. In the above aspect, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, and further preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, and may be 0 mass% or more.
The resin composition of the present invention may contain only 1 kind of other resin or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.
< polymerizable Compound >
The resin composition of the present invention preferably contains a polymerizable compound.
Examples of the polymerizable compound include a free-radical crosslinking agent and other crosslinking agents.
The resin composition of the present invention preferably contains a polymerizable compound having a boiling point of 200℃or higher at 1 atmosphere.
The boiling point is preferably 200℃or higher, more preferably 250℃or higher. The upper limit of the boiling point is not particularly limited, and may be, for example, 500℃or lower.
According to the above aspect, the amount of outgas generated can be reduced.
The polymerizable compound having a boiling point of 200 ℃ or higher at 1 atmosphere is preferably a compound having 3 or more polymerizable groups, more preferably a compound having 4 or more polymerizable groups, and still more preferably a compound having 5 or more polymerizable groups. The upper limit of the number of the polymerizable groups is not particularly limited, but is preferably 20 or less.
The polymerizable compound having a boiling point of 200 ℃ or higher at l atmospheric pressure is preferably a compound having 3 or more (meth) acrylate groups, more preferably a compound having 4 or more (meth) acrylate groups, and still more preferably a compound having 5 or more (meth) acrylate groups. The upper limit of the number of (meth) acrylate groups is not particularly limited, but is preferably 20 or less.
Specific examples of the polymerizable compound having a boiling point of 200℃or higher at 1 atmosphere include dipentaerythritol hexaacrylate, neopentyl tetraol tetraacrylate, neopentyl tetraol tetramethacrylate, ditrimethylolpropane tetraacrylate, ethoxylated dipentaerythritol polymethacrylate, and the like.
These compounds can be used as long as they have a boiling point of 200℃or higher, regardless of whether they are acrylic esters or methacrylic esters.
As these compounds, commercially available products can be used, and Shin-Nakamura Chemical co., ltd.
Further, from the viewpoint of suppressing the amount of outgas generated from the cured product, the resin composition preferably contains a polymerizable compound having an aliphatic ring structure.
The polymerizable compound may have only 1 polymerizable group, but preferably has 2 or more, more preferably has 2 to 10, still more preferably has 2 to 6, and particularly preferably has 4 to 6.
The aliphatic ring structure may be a saturated aliphatic ring structure or an unsaturated aliphatic ring structure.
The aliphatic ring structure may be a single ring or a heterocyclic ring such as a condensed ring, a crosslinked condensed ring, or a spiro ring.
Examples of the above-mentioned aliphatic ring structure include a cyclohexane structure, a cyclohexene structure, and a bicyclo [2.2.2] oct-5-ene structure.
[ free radical crosslinking agent ]
The resin composition of the present invention preferably contains a radical crosslinking agent.
The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth) acryloyl group, a maleimide group, and a (meth) acrylamide group.
Among them, the group containing an ethylenically unsaturated bond is preferably a (meth) acryloyl group, (meth) acrylamide group or vinylphenyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.
The radical crosslinking agent is preferably a compound having 1 or more ethylenically unsaturated bonds, more preferably a compound having 2 or more ethylenically unsaturated bonds. The radical crosslinking agent may have 3 or more ethylenically unsaturated bonds.
The compound having 2 or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and still more preferably a compound having 2 to 6 ethylenically unsaturated bonds.
Further, from the viewpoint of film strength of the obtained pattern (cured product), the resin composition of the present invention preferably further comprises a compound having 2 ethylenically unsaturated bonds and a compound having 3 or more ethylenically unsaturated bonds as described above.
The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
Specific examples of the radical polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, iconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters and amides thereof, and preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyvalent amine compounds. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, a sulfanyl group, or the like with a monofunctional or polyfunctional isocyanate or epoxy, a dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid, or the like can be preferably used. Further, addition reactants of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, thiols are preferable, and substitution reactants of unsaturated carboxylic acid esters or amides having releasable substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, thiols are more preferable. Further, as another example, a compound group substituted with an unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether, or the like may be used instead of the unsaturated carboxylic acid. For a specific example, reference is made to paragraphs 0113 to 0122 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.
The radical crosslinking agent is preferably a compound having a boiling point of 100 ℃ or higher at normal pressure. Examples thereof include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloxypropyl) ether, tris (acryloxyethyl) isocyanurate, glycerol, trimethylolethane, and the like, and a polyfunctional acrylate such as an epoxy acrylate or a polyfunctional acrylate which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then subjecting the resultant to (meth) acrylation, as disclosed in Japanese patent publication No. 48-041708, japanese patent publication No. 50-006034, japanese patent publication No. 51-037193, and as disclosed in Japanese patent publication No. 48-064183, japanese patent publication No. 49-043191, and Japanese patent publication No. 52-030490; and mixtures of these. Furthermore, the compounds described in paragraphs 0254 to 0257 of JP-A2008-292970 are also preferred. Further, a polyfunctional (meth) acrylate obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate, and the like can also be mentioned.
Further, as a preferable radical crosslinking agent other than the above, a compound having a fluorene ring and having 2 or more groups having an ethylenically unsaturated bond, and a cardo (cardo) resin described in japanese patent application laid-open publication No. 2010-160418, japanese patent application laid-open publication No. 2010-129825, japanese patent application laid-open publication No. 4364216, and the like can also be used.
Further, examples of the unsaturated compounds include specific unsaturated compounds described in Japanese patent publication No. 46-043946, japanese patent publication No. 01-040337 and Japanese patent publication No. 01-040336, and vinyl phosphonic acid compounds described in Japanese patent publication No. 02-025493. Furthermore, a perfluoroalkyl group-containing compound described in Japanese patent application laid-open No. 61-022048 can also be used. Furthermore, the compounds described as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol.20, no.7, pages 300 to 308 (1984) can also be used.
In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International publication No. 2015/199219, which are incorporated herein by reference, can be preferably used.
Further, the compounds described in JP-A-10-062986 as the specific examples of the compounds represented by the formulas (1) and (2) can also be used as the radical crosslinking agent, and the compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylating the resultant mixture.
Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese patent application laid-open No. 2015-187211 can also be used as radical crosslinking agents, and these are incorporated herein.
As the radical crosslinking agent, there are preferable a dipentaerythritol triacrylate (commercially available as KAYARAD D-330;Nippon Kayaku Co, manufactured by Ltd.), a dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320;Nippon Kayaku Co, manufactured by Ltd., A-TMMT; shin-Nakamura Chemical Co., manufactured by Itd.), a dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310;Nippon Kayaku Co, manufactured by Ltd.), a dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; nippon Kayaku Co., manufactured by Ltd., A-DPH; shin-Nakamura Chemical Co., manufactured by Ltd.), and a structure in which these (meth) acryloyl groups are bonded via an ethylene glycol residue or a propylene glycol residue. These oligomer types can also be used.
As commercial products of the radical crosslinking agent, for example, there may be mentioned a 4-functional acrylate SR-494 having 4 ethyleneoxy chains manufactured by Sartomer Company, inc, a 2-functional methacrylate Sartomer Company having 4 ethyleneoxy chains manufactured by Inc, SR-209, 231, 239, nippon Kayaku Co., ltd., a 6-functional acrylate DPCA-60 having 6 ethyleneoxy chains manufactured by Inc., a 3-functional acrylate TPA-330 having 3 isobutyleneoxy chains manufactured by Nippon Kayaku, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES Co., LTD.), NK ESTER NK M-40G, NK ESTER 4G, ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., ltd.), DPHA-40H (manufactured by Nippon Kayaku, ltd.), UA-306-35, UAS-35, UAB-140 (manufactured by LTD., LTD.), NK ESTER M-40G, NK ESTER M, NK (manufactured by NK-Nakamura Chemical Co., ltd.) and so on, and so on.
As the radical crosslinking agent, urethane acrylates described in Japanese patent publication No. 48-041708, japanese patent application laid-open No. 51-037193, japanese patent application laid-open No. 02-032293, and Japanese patent application laid-open No. 02-016765, urethane compounds having an ethylene oxide skeleton described in Japanese patent publication No. 58-049860, japanese patent publication No. 56-017654, japanese patent publication No. 62-039417, and Japanese patent publication No. 62-039418 are also preferred. Further, as the radical crosslinking agent, a compound having an amino structure or a thioether structure in the molecule described in JP-A-63-277653, JP-A-63-260909 or JP-A-01-105238 can be used.
The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to have an acid group. Particularly preferred are the following compounds: in the radical crosslinking agent in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to have an acid group, the aliphatic polyhydroxy compound is a compound of pentaerythritol or dipentaerythritol. Examples of commercial products include TOAGOSEI CO., LTD. Polyacid modified acrylic oligomers M-510 and M-520.
The radical crosslinking agent having an acid group preferably has an acid value of 0.1 to 300mgKOH/g, particularly preferably 1 to 100mgKOH/g. When the acid value of the radical crosslinking agent is within the above range, the workability in production is excellent, and further the developability is excellent. Furthermore, the polymerizability was good. The acid value was determined in accordance with JIS K0070: 1992, the measurement was performed.
From the viewpoints of resolution of the pattern and stretchability of the film, the resin composition preferably uses 2-functional methacrylate or acrylate.
Specific examples of the compound include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1, 5-pentanediol diacrylate, 1, 6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol a EO (ethylene oxide) adduct diacrylate, bisphenol a EO adduct dimethacrylate, bisphenol a PO adduct diacrylate, bisphenol a PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid diacrylate, isocyanuric acid modified dimethacrylate, other 2-functional methacrylates having urethane bonds, and other 2-functional methacrylates having urethane bonds. These may be used in combination of 2 or more kinds as required.
For example, PEG200 diacrylate refers to a polyethylene glycol diacrylate having a formula weight of about 200 in polyethylene glycol chains.
The resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as the radical crosslinking agent from the viewpoint of suppressing warpage accompanying control of the elastic modulus of a pattern (cured product). As the monofunctional radical crosslinking agent, there may be preferably used (meth) acrylic acid derivatives such as N-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, epoxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl glycidyl ether, and the like. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100 ℃ or higher at normal pressure is also preferable in order to suppress volatilization before exposure.
Examples of the radical crosslinking agent having a function of 2 or more include allyl compounds such as diallyl phthalate and triallyl trimellitate.
When the radical crosslinking agent is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 50 mass% or less, and still more preferably 30 mass% or less.
The radical crosslinking agent may be used alone or in combination of 1 or more than 2. When 2 or more kinds are used simultaneously, the total amount thereof is preferably within the above range.
[ other crosslinking Agents ]
The resin composition of the present invention preferably further comprises a crosslinking agent other than the radical crosslinking agent described above.
In the present invention, the other crosslinking agent means a crosslinking agent other than the radical crosslinking agent, and is preferably a compound having a plurality of groups in the molecule which promote a reaction to form covalent bonds with other compounds in the composition or reaction products thereof by the sensitization of the photoacid generator or photobase generator, and preferably a compound having a plurality of groups in the molecule which promote a reaction to form covalent bonds with other compounds in the composition or reaction products thereof by the action of an acid or a base.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
As the other crosslinking agent, a compound having at least 1 group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group, and an alkoxymethyl group is preferable, and a compound having a structure in which at least 1 group selected from the group consisting of an acyloxymethyl group, a hydroxymethyl group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferable.
Examples of the other crosslinking agent include compounds having the following structures: and a structure obtained by reacting an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, benzoguanamine, etc., with formaldehyde or formaldehyde and an alcohol to replace a hydrogen atom of the amino group with an acyloxymethyl group, a hydroxymethyl group, or an alkoxymethyl group. The method for producing these compounds is not particularly limited as long as they are compounds having the same structure as the compounds produced by the above method. The oligomer may be one in which methylol groups of these compounds are self-condensed with each other.
As the above amino group-containing compound, a crosslinking agent using melamine is referred to as a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is referred to as a urea-based crosslinking agent, a crosslinking agent using alkylene urea is referred to as an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is referred to as a benzoguanamine-based crosslinking agent.
Among these, the resin composition of the present invention preferably contains at least 1 compound selected from urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least 1 compound selected from acetylene urea-based crosslinking agents and melamine-based crosslinking agents described later.
Examples of the compound containing at least 1 of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of the urea structure described below, or a triazine.
The alkoxymethyl group or acyloxymethyl group contained in the above-mentioned compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and still more preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups in the above-mentioned compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
The molecular weight of the above compound is preferably 1500 or less, and preferably 180 to 1200.
[ chemical formula 34]
R 100 Represents an alkyl group or an acyl group.
R 101 R is R 102 Each independently represents a 1-valent organic group, and may be bonded to each other to form a ring.
Examples of the compound in which the alkoxymethyl group or the acyloxymethyl group is directly substituted on the aromatic group include compounds represented by the following general formula.
[ chemical formula 35]
Wherein X represents a single bond or a 2-valent organic group, each R 104 Each independently represents an alkyl group or an acyl group, R 103 Represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group which is decomposed by the action of an acid and generates an alkali-soluble group (e.g., a group which is detached by the action of an acid, a group which is cleaved by-C (R) 4 ) 2 COOR 5 A group (R) 4 R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms 5 Represents a group that is detached by the action of an acid. )).
R 105 Each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
Regarding the groups which are decomposed by the action of an acid to form alkali-soluble groups, the groups which are detached by the action of an acid are represented by-C (R 4 ) 2 COOR 5 R in the radicals represented 5 For example, there can be mentioned-C (R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 )、-C(R 01 )(R 02 )(OR 39 ) Etc.
Wherein R is 36 ～R 39 Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R is R 36 And R is R 37 Can be bonded to each other to form a ring.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
The alkyl group may be either a straight chain or a branched chain.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.
The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms.
The aralkyl group refers to an aryl group substituted with an alkyl group, and the preferable modes of the alkyl group and the aryl group are the same as those of the alkyl group and the aryl group.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.
Further, these groups may further have a known substituent within a range to obtain the effect of the present invention.
R 01 R is R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
As these groups, tertiary alkyl ester groups, acetal ester groups, cumyl ester groups, enol ester groups and the like are preferable. Further preferred is a tertiary alkyl ester group and an acetal ester group.
Specific examples of the compound having an alkoxymethyl group include the following structures. Examples of the compound having an acyloxymethyl group include compounds in which an alkoxymethyl group of the following compound is changed to an acyloxymethyl group. Examples of the compound having an alkoxymethyl group or an acyloxymethyl group in the molecule include, but are not limited to, the following compounds.
[ chemical formula 36]
[ chemical formula 37]
The compound containing at least 1 of an alkoxymethyl group and an acyloxymethyl group may be commercially available, or may be synthesized by a known method.
From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.
Specific examples of urea-based crosslinking agents include acetylene urea-based crosslinking agents such as monomethylolated acetylene urea, dimethylolated acetylene urea, trimethylolated acetylene urea, tetramethylolated acetylene urea, monomethylolated acetylene urea, dimethoxymethylated acetylene urea, trimethoxymethylated acetylene urea, tetramethoxymethylated acetylene urea, monomethylolated acetylene urea, dimethoxymethylated acetylene urea, trimethoxymethylated acetylene urea, tetraethoxymethylated acetylene urea, monopropoxylated methylated acetylene urea, dipropoxylated methylated acetylene urea, tripropoxylated methylated acetylene urea, tetrapropoxylated methylated acetylene urea, monobutyloxymethylacetylene urea, dibutoxymethylated acetylene urea, tributoxymethylacetylene urea or tetrabutoxymethylated acetylene urea;
Urea-based crosslinking agents such as dimethoxymethyl urea, diethoxymethyl urea, dipropoxymethyl urea and dibutoxymethyl urea,
Vinyl urea cross-linking agents such as mono-methylolated vinyl urea or di-methylolated vinyl urea, mono-methoxymethylated vinyl urea, di-methoxymethylated vinyl urea, mono-ethoxymethylated vinyl urea, di-ethoxymethylated vinyl urea, mono-propoxymethylated vinyl urea, di-propoxymethylated vinyl urea, mono-or di-butoxymethylated vinyl urea,
Propylene urea-based crosslinking agents such as monocrystaline propylene urea, dimethylol propylene urea, monomethoxy methylated propylene urea, dimethoxy methylated propylene urea, monoethoxy methylated propylene urea, diethoxy methylated propylene urea, monopropoxy methylated propylene urea, dipropoxy methylated propylene urea, monobutyl oxy methylated propylene urea or dibutoxy methylated propylene urea,
1, 3-bis (methoxymethyl) -4, 5-dihydroxy-2-imidazolidinone, 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone, and the like.
Specific examples of the benzoguanamine-based crosslinking agent include monomethylol benzoguanamine, dimethylol benzoguanamine, trimethylol benzoguanamine, tetramethylol benzoguanamine, monomethylol benzoguanamine, dimethoxymethyl benzoguanamine, trimethoxy methyl benzoguanamine, tetramethoxymethyl benzoguanamine, monomethoxymethyl benzoguanamine, dimethoxymethyl benzoguanamine, trimethoxy methyl benzoguanamine, tetraethoxymethyl benzoguanamine, monopropoxy methyl benzoguanamine, dipropoxy methyl benzoguanamine, tripropoxy methyl benzoguanamine, tetrapropoxy methyl benzoguanamine, dibutoxy methyl benzoguanamine, tributoxy methyl benzoguanamine, tetrabutoxy methyl benzoguanamine, and the like.
Further, as the compound having at least 1 group selected from the group consisting of hydroxymethyl and alkoxymethyl, a compound in which at least 1 group selected from the group consisting of hydroxymethyl and alkoxymethyl is directly bonded to an aromatic ring (preferably a benzene ring) may be preferably used.
Specific examples of such compounds include xylylene glycol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethyl benzene hydroxymethyl benzoate, bis (hydroxymethyl) biphenyl, dimethyl bis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethyl benzene methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, 4',4 "-ethylenetris [2, 6-bis (methoxymethyl) phenol ], 5' - [2, 2-trifluoro-1- (trifluoromethyl) ethylene ] bis [ 2-hydroxy-1, 3-benzenedimethanol ], 3', 5' -tetrakis (methoxymethyl) -1,1 '-biphenyl-4, 4' -diol, and the like.
As the other crosslinking agent, commercially available products can be used, and as a preferred commercially available product, examples thereof include 46DMOC, 46DMOEP (manufactured by ASAHI YUKIZAI CORPORATION above), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34-X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisoc-P, DMOM-PC DMOM-PTBP, DMOM-MBPC, triML-P, triML-35 XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (Honshu Chemical Industry Co., above), ltd), NIKALAC (registered trademark, the same as described below) MX-290, NIKALAC MX-280, NIKALAC MX-270, N [ KALAC MX-279, NIKALAC MW-1OOLM, NIKALAC MX-750LM (manufactured above by SANWA CHEMICALCO., LTD), and the like.
Further, the resin composition of the present invention preferably further contains at least 1 compound selected from the group consisting of an epoxy compound, an oxetane compound and a benzoxazine compound as another crosslinking agent.
Epoxy compound (epoxy group-containing compound)
As the epoxy compound, a compound having 2 or more epoxy groups in one molecule is preferable. The epoxy group undergoes a crosslinking reaction at 200 ℃ or less and does not cause dehydration reaction due to crosslinking, and thus film shrinkage is less likely to occur. Therefore, by containing the epoxy compound, the low-temperature curing and warpage of the resin composition of the present invention can be effectively suppressed.
The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further reduced, and warpage can be suppressed. Polyethylene oxide groups represent groups having a repeating unit number of 2 or more, preferably a repeating unit number of 2 to 15.
Examples of the epoxy compound include bisphenol a epoxy resins; bisphenol F type epoxy resin; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and the like, or polyhydric alcohol hydrocarbon type epoxy resins; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing polysilicones such as polymethylsiloxane (glycidoxypropyl) and the like, but are not limited thereto. Specifically, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are trade names, DIC Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESON (registered trademark) L-200 (trade name, new Japan Chemical co., ltd., manufacture), EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade name, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, epolate (registered trademark) GT401, epolate (registered trademark) PB4700, epolate (registered trademark) PB3600 (trade name, manufactured by Daicel Corporation, manufacture), NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3000, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (trade name, nippon Kayaku Co., ltd.) and the like. Moreover, the following compounds may also be preferably used.
[ chemical formula 38]
Wherein n is an integer of 1 to 5, and m is an integer of 1 to 20.
In the above structure, n is preferably 1 to 2 and m is preferably 3 to 7 from the viewpoint of both heat resistance and improvement of elongation.
Oxetane compounds (compounds having an oxetanyl group)
Examples of oxetane compounds include compounds having 2 or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyl oxetane, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexyl methyl) oxetane, and 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester. Specifically, TOAGOSEI CO., LTD. ARON OXETANE series (for example, OXT-121, OXT-221) may be preferably used, and these may be used alone or 2 or more kinds may be mixed.
Benzoxazine compound (compound having benzoxazolyl group)
The benzoxazine compound is preferable because it does not generate outgas during curing due to a crosslinking reaction caused by a ring-opening addition reaction, and further reduces heat shrinkage to suppress warpage.
Preferable examples of the benzoxazine compound include P-d type benzoxazine, F-a type benzoxazine (trade name, manufactured by Shikoku Chemicals Corporation), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac type dihydrobenzoxazine compounds. These may be used alone, or 2 or more kinds may be mixed.
The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition of the present invention. The other crosslinking agent may be contained only in 1 kind, or may be contained in 2 or more kinds. When the amount of the other thermal crosslinking agent is 2 or more, the total amount is preferably within the above range.
The resin composition of the present invention preferably contains a sensitizer.
Examples of the photosensitizer include a photopolymerization initiator and a photoacid generator, and a photopolymerization initiator is preferable.
[ polymerization initiator ]
The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it is preferable to include a photopolymerization initiator.
The photopolymerization initiator is preferably a photo radical polymerization initiator. The photo radical polymerization initiator is not particularly limited, and may be appropriately selected from known photo radical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays ranging from the ultraviolet region to the visible region is preferable. Moreover, it is possible to provide an active agent that exerts some action with the photosensitizing agent that is excited by light and generates active radicals.
The photo radical polymerization initiator preferably contains at least 1 initiator having a molecular weight of at least about 50 L.mol in a wavelength range of about 240 to 800nm (preferably 330 to 500 nm) -1 ·cm -1 A compound having a molar absorptivity. The molar absorptivity of the compound can be measured by a known method. For example, it is preferable to measure the concentration of the solvent at 0.01g/L by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, manufactured by Varian Co.) using ethyl acetate.
As the photo radical polymerization initiator, a known compound can be arbitrarily used. Examples thereof include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, and the like), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbisimidazole, oxime derivatives, and the like, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α -amino ketone compounds such as aminoacetophenone, α -hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For details of these, reference is made to paragraphs 0165 to 0182 of Japanese unexamined patent publication (Kokai) No. 2016-027357 and paragraphs 0138 to 0151 of International publication (Kokai) No. 2015/199219, which are incorporated herein by reference. Examples of the initiator include a compound described in JP-A-2014-130173 at the stage 0065-0111, JP-A-6301489, MATERIAL STAGE-60 p, vol.19, no.3, 2019, a peroxide-based photopolymerization initiator described in International publication No. 2018/221177, a photopolymerization initiator described in International publication No. 2018/110179, a photopolymerization initiator described in JP-A-2019-043864, a photopolymerization initiator described in JP-A-2019-044030, and a peroxide-based initiator described in JP-A-2019-167313, which are incorporated herein by reference.
Examples of the ketone compound include compounds described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, incorporated herein. Among the commercial products, KAYACURE DETX-S (Nippon Kayaku co., ltd.) is also preferably used.
In one embodiment of the present invention, as the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine oxide initiator described in JP-A-4225898 can be used, and the contents of these are incorporated in the present specification.
As the alpha-hydroxyketone initiator, omnirad 184, omnirad 1173, omnirad 2959, omnirad 127 (manufactured by IGM Resins B.V. above), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (manufactured by BASF corporation) can be used.
As the α -aminoketone initiator, omnirad 907, omnirad 369E, omnirad 379EG (manufactured by IGM Resins B.V. above), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF corporation) can be used.
As the aminoacetophenone initiator, a compound described in japanese patent application laid-open No. 2009-191179, which is incorporated herein by reference, can be used in which the absorption maximum wavelength is matched to a light source having a wavelength of 365nm or 405 nm.
Examples of the acylphosphine initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. As the catalyst, omnirad 819, omnirad TPO (manufactured by IGM Resins B.V. above), IRGACURE-819, IRGACURE-TPO (trade name: manufactured by BASF corporation) can be used.
Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF corporation), keycure VIS 813 (King Brother Chem Co., ltd.).
As the photo radical polymerization initiator, an oxime compound is more preferably exemplified. By using an oxime compound, the exposure latitude can be further effectively improved. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.
Specific examples of the oxime compound include a compound described in japanese patent application laid-open No. 2001-233846, a compound described in japanese patent application laid-open No. 2000-080068, a compound described in japanese patent application laid-open No. 2006-342166, a compound described in j.c.s.perkin II (1979, pages 1653-1660), a compound described in j.c.s.perkin II (1979, pages 156-162), a compound described in Journal of Photopolymer Scienee and Technology (1995, pages 202-232), a compound described in japanese patent application laid-open No. 2000-066385, a compound described in japanese patent application laid-open No. 2004-534797, a compound described in japanese patent application laid-open No. 2006-342166, a compound described in japanese patent application laid-open No. 6065596, a compound described in international publication No. 201153, a compound described in international publication No. 2017/680, a compound described in international publication No. 20157-1647, a compound described in international publication No. 2015-2015, a compound described in international publication No. 2015, etc.
Preferable oxime compounds include, for example, 3-benzoyloxy iminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxy iminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino1-phenylpropane-1-one, 2-benzoyloxy imino1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy imino1-phenylpropane-1-one having the following structures. In the resin composition of the present invention, an oxime compound (oxime-based photo radical polymerization initiator) is particularly preferably used as the photo radical polymerization initiator. The oxime-based photo-radical polymerization initiator has a linking group > c=n-O-C (=o) -, in the molecule.
[ chemical formula 39]
Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF corporation as described above), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION), and photo radical polymerization initiator 2 described in Japanese patent application laid-open No. 2012-014052 may also be preferably used. In addition, TR-PBG-304, TR-PBG-305 (Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (ADEKA CORPORATION). Further, DFI-091 (manufactured by Daito Chemix Corporation) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Furthermore, an oxime compound having the following structure can also be used.
[ chemical formula 40]
As the photo radical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include a compound described in japanese patent application laid-open No. 2014-137466 and a compound described in japanese patent No. 06636081, which are incorporated herein by reference.
As the photo radical polymerization initiator, an oxime compound having at least 1 benzene ring of carbazole ring as a skeleton of naphthalene ring can also be used. Specific examples of such oxime compounds include those described in international publication No. 2013/083505, which is incorporated herein by reference.
Oxime compounds having a fluorine atom can also be used. Specific examples of such oxime compounds include a compound described in JP 2010-26261028A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852A, and compound (C-3) described in paragraph 0101 of JP 2013-164471A, which are incorporated in the present specification.
As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably provided as a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of Japanese patent application laid-open No. 2013-114249, 0008 to 0012 and 0070 to 0079 of Japanese patent application laid-open No. 2014-137466, and 0007 to 0025 of Japanese patent application laid-open No. 4223071, which are incorporated herein by reference. Further, as the oxime compound having a nitro group, ADEKA ARKLS NCI-831 (ADEKA CORPORATION).
As the photo radical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples thereof include OE-01 to OE-75 described in International publication No. 2015/036910.
As the photo radical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International publication No. 2019/088055, which is incorporated herein by reference.
As the photopolymerization initiator, an aromatic ring group Ar having an electron withdrawing group introduced into an aromatic ring can also be used OX1 Is also referred to as oxime compound OX below. Ar as the above aromatic ring group OX1 Examples of the electron-withdrawing group include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, preferably an acyl group and a nitro group, more preferably an acyl group, and further preferably a benzoyl group, from the viewpoint of facilitating formation of a film excellent in light resistance. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic oxy group, alkenyl group, alkylmercapto group, arylmercapto group, acyl group or amino group, more preferably an alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic oxy group, alkylmercapto group, arylmercapto group or amino group, still more preferably an alkoxy group, alkylmercapto group or amino group.
The oxime compound OX is preferably at least 1 selected from the group consisting of a compound represented by the formula (OX 1) and a compound represented by the formula (OX 2), more preferably a compound represented by the formula (OX 2).
[ chemical formula 41]
Wherein R is X1 Represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylthio, arylalkylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyl, acyloxy, amino, phosphono, carbamoyl or sulfamoyl,
R X2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylsulfanyl, arylsulfanyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acyloxy or amino,
R X3 ～R X14 each independently represents a hydrogen atom or a substituent.
Wherein R is X10 ～R X14 At least 1 of which is an electron withdrawing group.
In the above formula, R is preferably X12 Is an electron withdrawing group and R X10 、R X11 、R X13 、R X14 Is a hydrogen atom.
Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of japanese patent No. 4600600, incorporated herein by reference.
Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in japanese patent application laid-open No. 2007-269779, an oxime compound having a thioaryl group shown in japanese patent application laid-open No. 2009-191061, and the like, which are incorporated herein by reference.
From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethyl ketal compounds, α -hydroxyketone compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron metal complexes and salts thereof, halomethyl oxadiazole compounds, 3-aryl substituted coumarin compounds.
More preferred photo radical polymerization initiator is a trihalomethyltriazine compound, an α -amino ketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, an acetophenone compound, still more preferably at least 1 compound selected from the group consisting of trihalomethyltriazine compound, α -amino ketone compound, metallocene compound, oxime compound, triarylimidazole dimer, benzophenone compound, still more preferably a metallocene compound or oxime compound.
The photo radical polymerization initiator may be a benzophenone, an aromatic ketone such as N, N ' -tetramethyl-4, 4' -diaminobenzophenone (Michler's ketone), an aromatic ketone such as N, N ' -tetraalkyl-4, 4' -diaminobenzophenone (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinophenone-1, a benzoin compound such as alkylanthraquinone, a benzoin alkyl ether, a benzoin compound such as benzoin, an alkyl benzoin, a benzyl derivative such as benzyl dimethyl ketal, or the like. Furthermore, a compound represented by the following formula (I) can also be used.
[ chemical formula 42]
In the formula (I), R I00 Is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by 1 or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by 1 or more oxygen atoms, and an alkyl unit having 1 to 18 carbon atoms4, at least 1 substituted phenyl or biphenyl group in the alkyl group of R I01 Is a group represented by formula (II) or is associated with R I00 The same radicals R I02 ～R I04 Each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.
[ chemical formula 43]
Wherein R is I05 ～R I07 R is the same as the R of the formula (I) I02 ～R I04 The same applies.
The photo radical polymerization initiator may be any one of the compounds described in paragraphs 0048 to 0055 of International publication No. 2015/125469, incorporated herein by reference.
As the photo radical polymerization initiator, a 2-functional or 3-functional or more photo radical polymerization initiator can be used. By using such a photo radical polymerization initiator, since 2 or more radicals are generated from one molecule of the photo radical polymerization initiator, good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, crystallinity is reduced, solubility in a solvent or the like is increased, and precipitation is less likely to occur with the passage of time, whereby the stability of the resin composition with time can be improved. Specific examples of the 2-functional or 3-functional or more photo-radical polymerization initiator include the photoinitiators of oxime esters described in Japanese patent application publication No. 2010-527339, japanese patent application publication No. 2011-524436, the photoinitiators described in Japanese patent application publication No. 0020-0033, the photoinitiators described in Japanese patent application publication No. 2017-0412, the dimers of oxime compounds described in Japanese patent application publication No. 0039-0055, the compounds (E) and (G) described in Japanese patent application publication No. 2013-522445, the Cmpd 1-7 described in Japanese patent application publication No. 2016/034963, the photoinitiators of oxime esters described in Japanese patent application publication No. 2017-523465, the photoinitiators described in Japanese patent application publication No. 0020-0033, the photoinitiators described in Japanese patent application publication No. 2017-151342, the photoinitiators described in paragraphs 0017-0026, the photoinitiators described in Japanese patent application publication No. 6469669, and the like.
When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass, relative to the total solid content of the resin composition of the present invention. The photopolymerization initiator may be contained in an amount of 1 or 2 or more. When the photopolymerization initiator is contained in an amount of 2 or more, the total amount is preferably within the above range.
In addition, the photopolymerization initiator may also function as a thermal polymerization initiator, and thus crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.
[ sensitizer ]
The resin composition may contain a sensitizer. The sensitizer absorbs a specific active radiation to be in an electron-excited state. The sensitizer in an electron excited state is brought into contact with a thermal radical polymerization initiator, a photo radical polymerization initiator or the like to perform the functions of electron transfer, energy transfer, heat generation or the like. Thus, the thermal radical polymerization initiator and the photo radical polymerization initiator cause chemical changes to decompose and generate radicals, acids or bases.
As the sensitizer that can be used, compounds such as benzophenone-based, milone-based, coumarin-based, pyrazole azo-based, aniline azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azo-methine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based can be used.
As the sensitizer, for example, examples thereof include midone, 4' -bis (diethylamino) benzophenone, 2, 5-bis (4 ' -diethylaminobenzylidene) cyclopentane, 2, 6-bis (4 ' -diethylaminobenzylidene) cyclohexanone, 2, 6-bis (4 ' -diethylaminobenzylidene) -4-methylcyclohexanone, 4' -bis (dimethylamino) chalcone, 4' -bis (diethylamino) chalcone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenyl biphenyl) -benzothiazole, 2- (p-dimethylaminophenyl vinylidene) benzothiazole, and 2- (p-dimethylaminophenylvinylene) isonaphthylthiazole, 1, 3-bis (4 ' -dimethylaminobenzylidene) acetone, 1, 3-bis (4 ' -diethylaminobenzylidene) acetone, 3' -carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7- (diethylamino) coumarin-3-carboxylic acid ethyl ester), and, N-phenyl-N ' -ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyrene) benzoxazole, 2- (p-dimethylaminostyrene) benzothiazole, 2- (p-dimethylaminostyrene) naphthalene (1, 2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4' -dimethylacetanilide, and the like.
Furthermore, other sensitizing colorants can be used.
For details of the sensitizing dye, reference is made to paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.
When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of at least 2 kinds.
[ chain transfer agent ]
The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in pages 683-684 of the third edition of the Polymer dictionary (university of Polymer (The Society of Polymer Science, japan) eds., 2005). As the chain transfer agent, for example, a chain transfer agent having-S-, -SO within the molecule can be used 2 -S-、-N-0-A group of compounds of SH, PH, siH and GeH, dithiobenzoate having thiocarbonylthio group for RAFT (Reversible Addition Fragmentation chain Transfer: reversible addition fragmentation chain transfer) polymerization, trithiocarbonate, dithiocarbamate, xanthate compound, etc. These supply hydrogen to the low activity radicals to generate radicals, or may generate radicals by deprotonation after oxidation. In particular, a thiol compound can be preferably used.
The chain transfer agent may be a compound described in paragraphs 0152 to 0153 of International publication No. 2015/199219, incorporated herein by reference.
When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition of the present invention. The chain transfer agent may be 1 or 2 or more. When the chain transfer agent is 2 or more, the total amount thereof is preferably within the above range.
< alkali Generator >
The resin composition of the present invention may contain a base generator. Here, the base generator means a compound capable of generating a base by physical action or chemical action. The base generator as referred to herein does not include the above specific resins. The alkali generator preferable for the resin composition of the present invention includes a thermal alkali generator and a photobase generator.
In particular, when the resin composition contains a precursor of the cyclized resin, the resin composition preferably contains a base generator. When the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be accelerated by heating, and the mechanical properties and chemical resistance of the cured product are improved, for example, the performance of the interlayer insulating film for a rewiring layer contained in a semiconductor package is improved.
The alkali generator may be an ionic alkali generator or a nonionic alkali generator.
Examples of the base generated from the base generator include secondary amines and tertiary amines.
The alkali generator of the present invention is not particularly limited, and a known alkali generator can be used. As the known base generating agent, for example, a carbamoyl oxime compound, a carbamoyl hydroxylamine compound, a carbamic acid compound, a carboxamide compound, an acetamide compound, a carbamic acid ester compound, a benzyl carbamic acid ester compound, a nitrobenzyl carbamic acid ester compound, a sulfonamide compound, an imidazole derivative compound, an amine imide compound, a pyridine derivative compound, an α -aminoacetophenone derivative compound, a quaternary ammonium salt derivative compound, a pyridinium salt, an α -lactone ring derivative compound, an amine imide compound, a phthalimide derivative compound, an acyloxyimide compound, or the like can be used.
Specific examples of the nonionic base generator include compounds represented by the formula (B1), the formula (B2) and the formula (B3).
[ chemical formula 44]
Rb in the formulae (B1) and (B2) 1 、Rb 2 Rb 3 Each independently is an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. Wherein Rb 1 Rb 2 And not simultaneously become hydrogen atoms. Furthermore, rb 1 、Rb 2 Rb 3 None of them has a carboxyl group. In the present specification, the tertiary amine structure means a structure in which all of 3 links of a 3-valent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the bonded carbon atom is a carbonyl group-forming carbon atom, that is, an amide group is formed together with a nitrogen atom, the present invention is not limited thereto.
In the formulae (B1) and (B2), rb is preferably 1 、Rb 2 Rb 3 At least 1 of which comprises a cyclic structure, more preferably at least 2 of which comprises a cyclic structure. The cyclic structure may be any of a single ring and a condensed ring, and a condensed ring formed by condensing a single ring or 2 single rings is preferable. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, preferably a 6-membered ring. The monocyclic ring is preferably cyclohexane ring or benzene ring, more preferablyCyclohexane rings are preferred.
More specifically, rb 1 Rb 2 Preferably, the compound is a hydrogen atom, an alkyl group (having a carbon number of preferably 1 to 24, more preferably 2 to 18, still more preferably 3 to 12), an alkenyl group (having a carbon number of preferably 2 to 24, more preferably 2 to 18, still more preferably 3 to 12), an aryl group (having a carbon number of preferably 6 to 22, more preferably 6 to 18, still more preferably 6 to 10), or an aralkyl group (having a carbon number of preferably 7 to 25, more preferably 7 to 19, still more preferably 7 to 12). These groups may have substituents within a range that exerts the effects of the present invention. Rb (Rb) 1 With Rb 2 Can be bonded to each other to form a ring. As the ring formed, a 4-to 7-membered nitrogen-containing heterocycle is preferable. In particular, rb 1 Rb 2 The substituent-containing linear, branched or cyclic alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) is preferable, the substituent-containing cycloalkyl group (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) is more preferable, and the substituent-containing cyclohexyl group is still more preferable.
As Rb 3 Examples thereof include an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), an aralkenyl group (preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), an alkoxy group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryloxy group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms) or an aralkoxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12). Among them, cycloalkyl groups (having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), aralkenyl groups, and aralkoxy groups are preferable. Rb (Rb) 3 Further, the substituent may be present within a range that exerts the effects of the present invention.
The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
[ chemical formula 45]
In the formula, rb 11 Rb 12 And Rb 31 Rb 32 Respectively with Rb in formula (B1) 1 Rb 2 The meaning is the same.
Rb 13 The alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), the alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), the aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), the aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms) may have a substituent in a range that exerts the effect of the present invention. Wherein Rb 13 Aralkyl groups are preferred.
Rb 33 Rb 34 Each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms), or a hydrogen atom.
Rb 35 The alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), the alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), the aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), the aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), and the aryl group are preferable.
The compound represented by the formula (B1-1) is also preferably a compound represented by the formula (B1-1 a).
[ chemical formula 46]
Rb 11 Rb 12 And Rb in formula (B1-1) 11 Rb 12 The meaning is the same.
Rb 15 Rb 16 The hydrogen atom, the alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), the alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms), the aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), the aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms), and the hydrogen atom or the methyl group are preferable.
Rb 17 The aryl group is preferably an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), an aralkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms).
[ chemical formula 47]
In the formula (B3), L is a 2-valent hydrocarbon group having a saturated hydrocarbon group on the path of the linking chain linking the adjacent oxygen atoms and carbon atoms, and represents a hydrocarbon group having 3 or more atoms on the path of the linking chain. And R is N1 R is R N2 Each independently represents a 1-valent organic group.
In the present specification, the term "link chain" refers to a chain in which the links are connected at the shortest distance (minimum number of atoms) among the atom chains on the path between 2 atoms or groups of atoms connecting the links. For example, in a compound represented by the following formula, L is composed of styrene and has a vinyl group as a saturated hydrocarbon group, the linking chain is composed of 4 carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "linking chain length") is 4.
[ chemical formula 48]
The number of carbon atoms in L of the formula (B3) (including carbon atoms other than the carbon atoms in the connecting chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. The upper limit of the chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less, from the viewpoint of rapidly proceeding the intramolecular cyclization reaction. In particular, the chain length of the linkage of L is preferably 4 or 5, and most preferably 4. Specific examples of preferred compounds for the base generator include, for example, compounds described in paragraphs 0102 to 0168 of International publication No. 2020/066416 and compounds described in paragraphs 0143 to 0177 of International publication No. 2018/038002.
The base generator preferably further comprises a compound represented by the following formula (N1).
[ chemical formula 49]
In the formula (N1), R N1 R is R N2 Each independently represents a 1-valent organic group, RC1 represents a hydrogen atom or a protecting group, and L represents a 2-valent linking group.
L is a 2-valent linking group, preferably a 2-valent organic group. The chain length of the linking group is preferably l or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The chain length refers to the number of atoms present in the atomic arrangement that forms the shortest path between 2 carbonyl groups in the formula.
In the formula (N1), R N1 R is R N2 Each independently is preferably a 1-valent organic group (the number of carbon atoms is preferably 1 to 24, more preferably 2 to 18, still more preferably 3 to 12), and the hydrocarbon group (the number of carbon atoms is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 10), specifically, an aliphatic hydrocarbon group (the number of carbon atoms is preferably 1 to 24, more preferably 1 to 12, still more preferably 1 to 10) or an aromatic hydrocarbon group (the number of carbon atoms is preferably 6 to 22, more preferably 6 to 18, still more preferably 6 to 10), and an aliphatic hydrocarbon group is preferable. As R N1 R is R N2 If an aliphatic hydrocarbon group is used, the alkali generated is preferably highly basic. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in an aliphatic hydrocarbon chain, an aromatic ring, or a substituent. In particular, an aliphatic hydrocarbon group having an oxygen atom in a hydrocarbon chain can be exemplified.
As a constituent R N1 R is R N2 Examples of the aliphatic hydrocarbon group(s) include a linear or branched alkyl group, a cyclic alkyl group, a group related to a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The number of carbon atoms of the linear or branched chain alkyl group is preferably 1 to 24, more preferably 2 to 18, and still more preferably 3 to 12. Examples of the linear or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl and the like.
The number of carbon atoms of the cyclic alkyl group is preferably 3 to 12, more preferably 3 to 6. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.
The number of carbon atoms of the group involved in the combination of the chain alkyl group and the cyclic alkyl group is preferably 4 to 24, more preferably 4 to 18, and still more preferably 4 to 12. Examples of the group involved in the combination of the chain alkyl group and the cyclic alkyl group include cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, ethylcyclohexylethyl group, and the like.
The number of carbon atoms of the alkyl group having an oxygen atom in the chain is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be linear or cyclic, or may be linear or branched.
Wherein R is from the viewpoint of increasing the boiling point of a base formed by decomposition to be described later N1 R is R N2 Preferably an alkyl group having 5 to 12 carbon atoms. Among them, in a formulation in which adhesion to a metal (e.g., copper) layer is important, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
R N1 R is R N2 Can be connected with each other to form a ring structure. When the cyclic structure is formed, an oxygen atom or the like may be present in the chain. And R is N1 R is R N2 The cyclic structure may be a single ring or a condensed ring, and is preferably a single ring. The cyclic structure to be formed is preferably a 5-or 6-membered ring containing a nitrogen atom in the formula (N1), and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring, and examples thereof include a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.
R C1 Represents a hydrogen atom or a protecting group, preferably a hydrogen atom.
The protecting group is preferably a protecting group which is decomposed by the action of an acid or a base, and a protecting group which is decomposed by an acid is preferable.
Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. Examples of the chain or cyclic alkyl group include methyl, ethyl, isopropyl, t-butyl, and cyclohexyl. The chain alkyl group having an oxygen atom in the chain includes, specifically, an alkoxyalkyl group, and more specifically, a methoxymethyl group (MOM), an ethoxyethyl group (EE), and the like. Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, an epoxypropyl group, an oxetanyl group, a tetrahydrofuranyl group, and a Tetrahydropyran (THP) group.
The 2-valent linking group constituting L is not particularly limited, and is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent, and may have a kind of atom other than a carbon atom in the hydrocarbon chain. More specifically, a 2-valent hydrocarbon linking group which may have an oxygen atom in the chain is preferable, a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a 2-valent aromatic hydrocarbon group, or a group related to a combination of a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a 2-valent aromatic hydrocarbon group is more preferable, and a 2-valent aliphatic hydrocarbon group which may have an oxygen atom in the chain is further preferable. These groups preferably do not have an oxygen atom.
The number of carbon atoms of the 2-valent hydrocarbon linking group is preferably 1 to 24, more preferably 2 to 12, and still more preferably 2 to 6. The number of carbon atoms of the 2-valent aliphatic hydrocarbon group is preferably 1 to 12, more preferably 2 to 6, and still more preferably 2 to 4. The number of carbon atoms of the 2-valent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and still more preferably 6 to 10. The number of carbon atoms of the group (for example, an arylene alkyl group) involved in the combination of the 2-valent aliphatic hydrocarbon group and the 2-valent aromatic hydrocarbon group is preferably 7 to 22, more preferably 7 to 18, and still more preferably 7 to 10.
The linking group L is preferably a linear or branched chain alkylene group, a cyclic alkylene group, a group related to a combination of a chain alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, or an arylene alkylene group.
The number of carbon atoms of the linear or branched chain alkylene group is preferably 1 to 12, more preferably 2 to 6, and still more preferably 2 to 4.
The number of carbon atoms of the cyclic alkylene group is preferably 3 to 12, more preferably 3 to 6.
The number of carbon atoms of the group involved in the combination of the chain alkylene group and the cyclic alkylene group is preferably 4 to 24, more preferably 4 to 12, and still more preferably 4 to 6.
The alkylene group having an oxygen atom in the chain may be linear or cyclic, or may be linear or branched. The number of carbon atoms of the alkylene group having an oxygen atom in the chain is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 3.
The number of carbon atoms of the linear or branched alkenyl group is preferably 2 to 12, more preferably 2 to 6, and still more preferably 2 to 3. The number of c=c bonds of the linear or branched chain alkenylene group is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3.
The number of carbon atoms of the cyclic alkenylene group is preferably 3 to 12, more preferably 3 to 6. The number of c=c bonds of the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 2.
The number of carbon atoms of the arylene group is preferably 6 to 22, more preferably 6 to 18, and still more preferably 6 to 10.
The number of carbon atoms of the arylene alkylene is preferably 7 to 23, more preferably 7 to 19, and still more preferably 7 to 11.
Among them, preferred are chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, chain alkenylene groups, arylene groups, and arylene alkylene groups, and more preferred are 1, 2-vinyl groups, propane diyl groups (particularly 1, 3-propane diyl groups), cyclohexane diyl groups (particularly 1, 2-cyclohexane diyl groups), vinylidene groups (particularly cis-vinylidene groups), phenylene groups (1, 2-phenylene groups), phenylene methylene groups (particularly 1, 2-phenylene methylene groups), and ethyleneoxy vinyl groups (particularly 1, 2-ethyleneoxy-1, 2-vinyl groups).
The following examples are given as examples of the alkali generator, but the present invention should not be construed as being limited thereto.
[ chemical formula 50]
The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.
Specific examples of preferred compounds for the ionic base generator include compounds described in paragraphs 0148 to 0163 of International publication No. 2018/038002.
Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto.
[ chemical formula 51]
Specific examples of the imide salt include the following compounds, but the present invention is not limited thereto.
[ chemical formula 52]
When the resin composition of the present invention contains the alkali generator, the content of the alkali generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and still more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
The alkali generator can be used in an amount of 1 or 2 or more. When 2 or more kinds are used, the total amount is preferably within the above range.
As described above, in the present invention, a base may be generated from a specific resin or a developer or a treatment liquid may be allowed to contain a base or a base generator and permeate into a film.
Thus, the following design is possible: the content of the base generator is reduced as compared with a conventional resin composition comprising the base generator and the cyclized resin or a precursor thereof. As a result, it is considered that the residue of the alkali generator after the generation of the alkali, the undegraded alkali generator itself, and the like are less likely to remain in the composition, the amount of outgas generated from the cured product is reduced, and the adhesion in the cured product is also improved.
In such a mode, it is also preferable to set the content of the base generator to 2 mass% or less with respect to 100 parts by mass of the resin. Further, the content of the alkali generator is preferably set to 1 mass% or less, and more preferably set to 0.5 mass% or less, based on 100 parts by mass of the resin. The content of the alkali generator is preferably set to 0.1 mass% or less based on 100 parts by mass of the resin. In these modes, the lower limit of the content of the base generator may be 0 mass%.
The content of the alkali generator can be determined according to the kind and amount of alkali generated from the specific resin, the kind and amount of alkali contained in the developer or the treatment liquid, heating conditions, and the like.
< solvent >
The resin composition of the present invention preferably contains a solvent.
The solvent may be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, alcohols, and the like.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetate (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-ethoxypropionate, ethyl 2-alkoxy-2-methyl propionate, and ethyl 2-alkoxypropionate, etc.), methyl 2-alkoxypropionate, methyl 2-ethoxypropionate, etc.), methyl 2-alkoxypropionate, etc. (e.g., methyl 2-ethoxypropionate, etc.), ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl caproate, ethyl heptanoate, dimethyl malonate, diethyl malonate, and the like.
As the ethers, for example, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether, and the like can be preferably used.
Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-methylcyclohexanone, l-glucosone (levoglucosenone), and dihydro-l-glucosone.
Examples of the cyclic hydrocarbon include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.
As the sulfoxide, dimethyl sulfoxide is preferable, for example.
As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, N-dimethylisobutyramide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like can be preferably used.
Preferred examples of the urea include N, N, N ', N' -tetramethylurea and 1, 3-dimethyl-2-imidazolidinone.
Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl benzyl alcohol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
The solvent is preferably mixed with 2 or more types from the viewpoint of improvement of the properties of the coated surface.
In the present invention, it is preferable that the solvent be 1 or a mixed solvent of 2 or more solvents selected from methyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether acetate, levoglucosone, and dihydro-levoglucosone. It is particularly preferred to use dimethyl sulfoxide and gamma-butyrolactone simultaneously or N-methyl-2-pyrrolidone and ethyl lactate simultaneously.
The solvent content is preferably 5 to 80% by mass, more preferably 5 to 75% by mass, still more preferably 10 to 70% by mass, and still more preferably 20 to 70% by mass of the total solid content concentration of the resin composition of the present invention from the viewpoint of coatability. The solvent content is adjusted according to the thickness and coating method required by the coating film.
The resin composition of the present invention may contain only 1 solvent, or may contain 2 or more solvents. When the solvent is contained in an amount of 2 or more, the total amount thereof is preferably within the above range.
< Metal adhesion improver >
The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for an electrode, wiring, or the like. Examples of the metal adhesion improving agent include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion promoter, a titanium-based adhesion promoter, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β -keto ester compound, an amino compound, and the like.
[ silane coupling agent ]
Examples of the silane coupling agent include a compound described in paragraph 0167 of Japanese patent application laid-open No. 2015/199219, a compound described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, a compound described in paragraphs 0063 to 0071 of International patent application laid-open No. 2011/080992, a compound described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, a compound described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014/097594, a compound described in paragraphs 2017 to 0078 of Japanese patent application laid-open No. 2018-173573, and the like. Further, as described in paragraphs 0050 to 0058 of JP-A2011-128358, it is also preferable to use 2 or more different silane coupling agents. Furthermore, the following compounds are also preferably used as the silane coupling agent. In the following formula, me represents methyl group, and Et represents ethyl group.
[ chemical formula 53]
Examples of the other silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidenepropylamine, N-phenyl-3-aminopropyltrimethoxysilane, trimethoxysilyl, 3-trimethoxypropyl-isocyanurate, 3-methoxypropylpropyltrimethoxysilane, 3-mercaptopropyl silane, mercapto-3-ethoxypropyl silane, mercapto-3-propyl-methoxypropyl silane, mercapto-3-propyl-3-propylmercapto-propyl-silane, mercapto-propyl-3-propyl-methyl-3-ethoxysilyl-3-triethoxysilane, and the like, 3-trimethoxysilylpropyl succinic anhydride. These can be used singly or in combination of 1 or more than 2.
[ aluminum series adhesive auxiliary agent ]
Examples of the aluminum-based adhesive auxiliary agent include aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum ethylacetoacetate diisopropyl ester, and the like.
Further, as other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP-A2014-186186 and thioether compounds described in paragraphs 0032 to 0043 of JP-A2013-072935 can be used, and these are incorporated herein.
The content of the metal adhesion improver is preferably in the range of 0.01 to 30 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. When the lower limit value is not less than the upper limit value, the adhesion between the pattern and the metal layer is improved, and when the upper limit value is not more than the upper limit value, the heat resistance and mechanical properties of the pattern are improved. The metal adhesion improver may be 1 or 2 or more. When 2 or more kinds are used, the total thereof is preferably within the above range.
< migration inhibitor >
The resin composition of the present invention also preferably contains a migration inhibitor. By including the migration inhibitor, transfer of metal ions originating from the metal layer (metal wiring) into the film can be effectively suppressed.
The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thiourea and mercapto groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2, 4-triazole, benzotriazole, 3-amino-1, 2, 4-triazole, and 3, 5-diamino-1, 2, 4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.
Alternatively, an ion scavenger that traps anions such as halide ions can be used.
As other migration inhibitors, rust inhibitors described in paragraph 0094 of japanese patent application laid-open publication No. 2013-015701, compounds described in paragraphs 0073-0076 of japanese patent application laid-open publication No. 2009-283711, compounds described in paragraph 0052 of japanese patent application laid-open publication No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of japanese patent application laid-open publication No. 2012-194520, compounds described in paragraph 0166 of international publication No. 2015/199219, and the like can be used, and these are incorporated into the present specification.
Specific examples of migration inhibitors include the following compounds.
[ chemical formula 54]
When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass% relative to the total solid content of the resin composition of the present invention.
The migration inhibitor may be 1 or 2 or more. When the migration inhibitor is 2 or more, the total thereof is preferably within the above range.
< polymerization inhibitor >
The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenol compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.
As specific compounds of the polymerization inhibitor, p-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol (pyrogallol), p-t-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxylamine cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6-di-t-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthalene) hydroxylamine ammonium salt, bis (4-hydroxy-3, 5-t-butyl-4-methylphenol, 5-nitroso-5-hydroxy-3, 3-hydroxy-benzyl-4, 3H-tri-4, 3H-hydroxybenzyl ketone, 3, 5H-tri-4-hydroxy-3H-3, 5-t-butyl-4-hydroxy-methyl-4, 2, 6-tetramethylpiperidine 1-oxyl, 2, 6-tetramethylpiperidine 1-oxyl, phenothiazine, phenazine, 1-diphenyl-2-picrylhydrazine, copper (II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like. Further, a polymerization inhibitor described in paragraph 0060 of Japanese patent application laid-open No. 2015-127817 and a compound described in paragraphs 0031 to 0046 of International publication No. 2015/125469, which are incorporated herein by reference, can also be used.
When the resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition of the present invention.
The polymerization inhibitor may be 1 or 2 or more. When the polymerization inhibitor is 2 or more, the total amount thereof is preferably within the above range.
< other additives >
The resin composition of the present invention can be blended with various additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymer compounds, plasticizers, other assistants (e.g., defoamers, flame retardants, etc.) and the like as required within the range that achieves the effects of the present invention. By properly containing these components, properties such as film physical properties can be adjusted. For these components, for example, reference can be made to the descriptions of paragraphs 0183 and later of Japanese patent application laid-open No. 2012-003225 (paragraph 0237 of the specification of corresponding U.S. patent application publication No. 2013/0034812), and the descriptions of paragraphs 0101 to 0104 and 0107 to 0109 of Japanese patent application laid-open No. 2008-250074, and the like, which are incorporated herein by reference. When these additives are blended, the total blending amount is preferably 3 mass% or less of the solid content of the resin composition of the present invention.
[ surfactant ]
As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
By adding the surfactant to the resin composition of the present invention, the liquid properties (particularly fluidity) when the resin composition is prepared into a coating liquid can be further improved, and the uniformity of the coating thickness and the liquid saving property can be further improved. That is, when a film is formed using a coating liquid to which a surfactant-containing composition is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, thereby improving wettability to the surface to be coated and improving coatability to the surface to be coated. Therefore, a film having a uniform thickness with less thickness unevenness can be further preferably formed.
Examples of the fluorine-based surfactant include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (manufactured by DIC Corporation above), fluoro FC430, fluoro FC431, fluoro FC171, novec FC4430, novec FC4432 (manufactured by 3M Japan Limited above), surflon S-382, surflon SC-101, surflon SC-103, surflon SC-104, surflon SC-105, surflon SC-1068, surflon SC-381, surflon SC-383, surflon S-40 (manufactured by DIC Corporation above), surfon FC431, fluold FC171, novelon FC4430 (manufactured by 3M Japanese Limited above), surflon SC-105, surflon SC-381, surfon SC-383, surfon S-40 (manufactured by Urfon, UF 656, PF) and PF 20, PF656 manufactured by NOF. The fluorine-based surfactant may be any of the compounds described in paragraphs 0015 to 0158 of Japanese patent application laid-open No. 2015-117327 and the compounds described in paragraphs 0117 to 0132 of Japanese patent application laid-open No. 2011-132503, which are incorporated herein by reference. As the fluorine-based surfactant, a block polymer can be used, and specific examples thereof include compounds described in japanese patent application laid-open publication No. 2011-89090, which are incorporated herein.
The fluorine-containing surfactant may also preferably be a fluorine-containing polymer compound containing a repeating unit derived from a (meth) acrylate compound having a fluorine atom and a repeating unit derived from a (meth) acrylate compound having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group).
[ chemical formula 55]
The weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A2010-164965, which are incorporated herein by reference. Examples of commercial products include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.
The fluorine content of the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-containing surfactant having a fluorine content within this range is effective in uniformity of thickness of the coating film and liquid saving property, and has good solubility in the composition.
Examples of silicone surfactants include Toray Silicone DC PA, toray Silicone SH PA, toray Silicone DC PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH PA, toray Silicone SH8400 (manufactured by ltd. Above), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials inc. Above), KP-341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical co. Above, ltd. Above), BYK307, BYK323, BYK330 (manufactured by BYK Chemie GmbH) above, and the like.
Examples of hydrocarbon surfactants include PIONIN A-76, NEWKALGEN FS-3PG, PIONIN B-709, PIONIN B-8l1-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, PIONIN P-4050-T (the above is TAKEMOTO OIL FAT CO., LTD).
Examples of the nonionic surfactant include glycerin, trimethylol propane, trimethylol ethane, and ethoxylates and propoxylates thereof (for example, glycerin propoxylate, glycerin ethoxylate, and the like), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Examples of the commercial products include PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF corporation), tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF corporation), solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTOOL & FAT CO., LTD), OLFIN E1010, surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry CO., ltd.), and the like.
Specific examples of the cationic surfactant include organosiloxane polymers KP-341 (Shin-Etsu Chemical Co., ltd.), (meth) acrylic (co) polymers POLYFLOW No.75, no.77, no.90, N0.95 (Kyoeisha Chemical Co., ltd.), W001 (Yusho Co., ltd.), and the like.
Specific examples of the anionic surfactant include W004, W005, W017 (Yusho co., ltd.), and saldet BL (manufactured by SANYO KASEI co.ltd.).
The surfactant may be used in an amount of 1 kind or 2 kinds or more.
The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
[ higher fatty acid derivative ]
In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the resin composition of the present invention so as to be biased to the surface of the resin composition of the present invention during drying after coating.
The higher fatty acid derivative may be a compound described in paragraph 0155 of International publication No. 2015/199219, which is incorporated herein by reference.
When the resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. The number of higher fatty acid derivatives may be 1 or 2 or more. When the number of higher fatty acid derivatives is 2 or more, the total thereof is preferably within the above range.
[ thermal polymerization initiator ]
The resin composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a compound having polymerizability. The addition of the thermal radical polymerization initiator can further progress the polymerization reaction of the resin and the polymerizable compound, and therefore can further improve the solvent resistance. The photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese patent application laid-open No. 2008-063254, the contents of which are incorporated herein by reference.
When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, relative to the total solid content of the resin composition of the present invention. The thermal polymerization initiator may be contained in an amount of 1 or 2 or more. When the thermal polymerization initiator is contained in an amount of 2 or more, the total amount is preferably within the above range.
[ inorganic particles ]
The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.
The average particle diameter of the inorganic particles is preferably 0.01 to 2.0. Mu.m, more preferably 0.02 to 1.5. Mu.m, still more preferably 0.03 to 1.0. Mu.m, particularly preferably 0.04 to 0.5. Mu.m.
The average particle diameter of the inorganic particles is a primary particle diameter and is a volume average particle diameter. The volume average particle diameter can be measured by a dynamic light scattering method based on Nanotrac WAVE II EX-150 (NIKKISO co., ltd.).
If the above measurement is difficult, the measurement can be performed by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/scattering method.
[ ultraviolet absorber ]
The resin composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other ultraviolet absorbers can be used.
Examples of the salicylate-based ultraviolet light absorber include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate, and examples of the benzophenone-based ultraviolet light absorber include 2,2' -dihydroxy-4-methoxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2', 4' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of the benzotriazole-based ultraviolet absorber include 2- (2 '-hydroxy-3', 5 '-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 '-t-butyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -t-amyl-5 '-isobutylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 '-isobutyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -isobutyl-5 '-propylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-t-butylphenyl) benzotriazole, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, and 2- [2 '-hydroxy-5' - (1, 3-tetramethyl) phenyl ] benzotriazole.
Examples of the substituted acrylonitrile ultraviolet absorber include ethyl 2-cyano-3, 3-diphenylacrylate and 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate. Further, examples of the triazine-based ultraviolet light absorber include mono (hydroxyphenyl) triazine compounds such as 2- [4- [ (2-hydroxy-3-dodecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- [ (2-hydroxy-3-tridecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, and 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine; bis (hydroxyphenyl) triazine compounds such as 2, 4-bis (2-hydroxy-4-propoxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine, 2, 4-bis (2-hydroxy-3-methyl-4-propoxyphenyl) -6- (4-methylphenyl) -1,3, 5-triazine, and 2, 4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine; tris (hydroxyphenyl) triazine compounds such as 2, 4-bis (2-hydroxy-4-butoxyphenyl) -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-octyloxyphenyl) -1,3, 5-triazine, and 2,4, 6-tris [ 2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl ] -1,3, 5-triazine.
In the present invention, 1 kind of the above-mentioned various ultraviolet absorbers may be used alone, or 2 or more kinds may be used in combination.
The composition of the present invention may or may not contain an ultraviolet absorber, but when contained, the content of the ultraviolet absorber is preferably 0.001 mass% or more and 1 mass% or less, more preferably 0.01 mass% or more and 0.1 mass% or less, relative to the total solid content mass of the composition of the present invention.
[ organic titanium Compound ]
The resin composition of the present embodiment may contain an organic titanium compound. By containing the organic titanium compound in the resin composition, a resin layer excellent in chemical resistance can be formed even when cured at a low temperature.
Examples of the usable organic titanium compound include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in the following I) to VII).
I) Chelating titanium compound: among them, a chelate titanium compound having 2 or more alkoxy groups is more preferable in view of excellent storage stability of the resin composition and obtaining a good cured pattern. Specific examples are titanium bis (triethanolamine) diisopropoxide, titanium bis (n-butoxy) bis (2, 4-glutarate) diisopropoxide bis (2, 4-glutarate) titanium, titanium diisopropoxide bis (tetramethylheptanedioate) titanium, titanium diisopropoxide bis (ethylacetoacetate), and the like.
II) a titanium tetraalkoxide compound: examples of the titanium include tetra (n-butoxy) titanium, tetraethoxy titanium, tetra (2-ethylhexyl) titanium, tetraisobutoxy titanium, tetraisopropoxy titanium, tetramethoxy titanium, tetramethoxypropoxy titanium, tetramethylphenoxy titanium, tetra (n-nonoxy) titanium, tetra (n-propoxy) titanium, tetrastearoxy titanium, and tetra [ bis {2,2- (allyloxymethyl) propoxy } ] titanium.
III) titanocene compound: for example, pentamethylcyclopentadienyl trimethoxytitanium, bis (. Eta.5-2, 4-cyclopenta-1-yl) bis (2, 6-difluorophenyl) titanium, bis (. Eta.5-2, 4-cyclopenta-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, and the like.
IV) monoalkoxytitanium compounds: for example, titanium isopropoxide, such as dioctyl phosphate, and titanium isopropoxide, such as dodecylbenzenesulfonate.
V) titanium oxide compound: examples of the compound include titanium oxide bis (glutarate), titanium oxide bis (tetramethylpimelate), and titanium oxide phthalocyanine.
VI) titanium tetra acetylacetonate compound: for example, titanium tetraacetylacetonate.
VII) titanate coupling agent: for example, isopropyl tridecyl benzenesulfonyl titanate, etc.
Among them, the organic titanium compound is preferably at least 1 compound selected from the group consisting of the above-mentioned I) chelate titanium compound, II) tetraalkoxy titanium compound and III) titanocene compound, from the viewpoint of exhibiting more excellent chemical resistance. Particularly preferred are diisopropoxybis (ethylacetoacetate) titanium, tetra (n-butoxy) titanium and bis (. Eta.5-2, 4-cyclopenta-n-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium.
When the organic titanium compound is blended, the blending amount thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the blending amount is 0.05 parts by mass or more, the obtained cured pattern more effectively exhibits good heat resistance and chemical resistance, while when 10 parts by mass or less, the composition is more excellent in storage stability.
[ antioxidant ]
The resin composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the tensile properties of the cured film and the adhesion to a metal material can be improved. Examples of the antioxidant include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferred examples of the phenol compound include hindered phenol compounds. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) are preferred. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Furthermore, the antioxidant is preferably a compound having a phenol group and a phosphite group in the same molecule. Further, the antioxidant can also preferably be a phosphorus-based antioxidant. Examples of phosphorus antioxidants include tris [2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxaphosphen-hepta-6-yl ] oxy ] ethyl ] amine, tris [2- [ (4, 6,9, 11-tetra-t-butyldibenzo [ d, f ] [1,3,2] dioxaphosphen-2-yl) oxy ] ethyl ] amine, and ethyl bis (2, 4-di-t-butyl-6-methylphenyl) phosphite. Examples of the commercially available antioxidants include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50F, ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (manufactured by ADEKA CORPORATION). The antioxidant may be a compound described in paragraphs 0023 to 0048 of Japanese patent No. 6268967, incorporated herein by reference. Further, the resin composition of the present invention may contain a latent antioxidant as needed. As potential antioxidants, the following compounds may be mentioned: a compound which functions as an antioxidant by protecting a site functioning as an antioxidant with a protecting group and releasing the protecting group by heating at 100 to 250 ℃ or heating at 80 to 200 ℃ in the presence of an acid/base catalyst. Examples of the potential antioxidant include compounds described in International publication No. 2014/021023, international publication No. 2017/030005, and Japanese patent application laid-open No. 2017-008219, which are incorporated herein by reference. Examples of commercial products of the latent antioxidant include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).
Examples of the preferable antioxidant include 2, 2-thiobis (4-methyl-6-t-butylphenol), 2, 6-di-t-butylphenol, and a compound represented by formula (3).
[ chemical formula 56]
In the general formula (3), R 5 Represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), R 6 An alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). R is R 7 Represents a 1-to 4-valent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer of 1 to 4.
The compound represented by formula (3) suppresses oxidative degradation of the aliphatic group and the phenolic hydroxyl group of the resin. Further, by the rust prevention effect on the metal material, oxidation of the metal can be suppressed.
In order to be able to act on both the resin and the metal material, k is more preferably an integer of 2 to 4. As R 7 Examples thereof include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, groups obtained by combining these groups, and the like, and may further have a substituent. Among them, alkyl ether and-NH-are preferable from the viewpoints of solubility in a developer and metal adhesion, and-NH-is more preferable from the viewpoints of interaction with a resin and metal adhesion due to formation of a metal complex.
Examples of the compound represented by the general formula (3) include, but are not limited to, the following structures.
[ chemical formula 57]
[ chemical formula 58]
[ chemical formula 59]
[ chemical formula 60]
The amount of the antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. By setting the addition amount to 0.1 part by mass or more, the effect of improving the adhesion to a metal material can be easily obtained by the stretching property even under a high-temperature and high-humidity environment, and by setting the addition amount to 10 parts by mass or less, for example, the sensitivity of the resin composition can be improved by the interaction with a sensitizer. The antioxidant may be used in an amount of 1 or 2 or more. When 2 or more kinds are used, the total amount thereof is preferably within the above range.
[ anti-coagulant ]
The resin composition of the present embodiment may contain an anti-coagulant as necessary. Examples of the anti-caking agent include sodium polyacrylate.
In the present invention, 1 anticoagulant may be used alone, or 2 or more anticoagulants may be used in combination.
The resin composition of the present invention may or may not contain an anti-coagulant, but when contained, the content of the anti-coagulant is preferably 0.01 mass% or more and 10 mass% or less, more preferably 0.02 mass% or more and 5 mass% or less, relative to the total solid content mass of the resin composition of the present invention.
[ phenol Compounds ]
The resin composition of the present embodiment may contain a phenolic compound as needed. Examples of the phenolic compound include Bis-Z, bisP-EZ, tekP-4HBPA, trisP-HAP, trisP-PA, bisOCHP-Z, bisP-MZ, bisP-PZ, bisP-IPZ, bisOCP-IPZ, bisP-CP, bisRS-2P, bisRS-3P, bisP-OCHP, methyl Tris-FR-CR, bisRS-26X (trade name, honshu Chemical Industry Co., ltd.), BIP-PC, BIR-PTBP, BIR-BIPC-F (trade name, ASAHI YUKIZAI CORPORATION).
In the present invention, 1 kind of phenol compound may be used alone, or 2 or more kinds may be used in combination.
The resin composition of the present invention may or may not contain a phenolic compound, but when contained, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less, relative to the total solid content mass of the resin composition of the present invention.
[ other Polymer Compounds ]
Examples of the other polymer compound include a silicone resin, a (meth) acrylic polymer copolymerized with (meth) acrylic acid, a novolak resin, a resol resin, a polyhydroxystyrene resin, and a copolymer of these. The other polymer compound may be modified body having a crosslinking group such as a hydroxymethyl group, an alkoxymethyl group, or an epoxy group introduced therein.
In the present invention, 1 or 2 or more other polymer compounds may be used alone or in combination.
The resin composition of the present invention may or may not contain other polymer compounds, but when contained, the content of other polymer compounds is preferably 0.01 mass% or more and 30 mass% or less, more preferably 0.02 mass% or more and 20 mass% or less, relative to the total solid content mass of the resin composition of the present invention.
< Properties of resin composition >
The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, it is preferably 1,000mm 2 /s～12,000mm 2 S, more preferably 2,000mm 2 /s～10,000mm 2 S, more preferably 2,500mm 2 /s～8,000mm 2 And/s. When the amount is within the above range, a coating film having high uniformity can be easily obtained. For example, if it is 1,000mm 2 At least one of the above, the wiring is easy to be used for rewiringThe thickness of the insulating film is 12,000mm when the film is coated 2 A coating film having an excellent coating surface shape can be obtained.
< restriction of substances contained in resin composition >
The water content of the resin composition of the present invention is preferably less than 2.0 mass%, more preferably less than 1.5 mass%, and even more preferably less than 1.0 mass%. When the content is less than 2.0%, the storage stability of the resin composition is improved.
Examples of the method for maintaining the water content include humidity adjustment under storage conditions and reduction of porosity of the storage container during storage.
From the viewpoint of insulation properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million (parts per million)), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, and the like, except for metals contained as a complex of an organic compound and a metal. When a plurality of metals are contained, the total of these metals is preferably within the above range.
Further, as a method for reducing metal impurities accidentally contained in the resin composition of the present invention, the following method can be mentioned: the raw materials having a small metal content are selected as the raw materials constituting the resin composition of the present invention, the raw materials constituting the resin composition of the present invention are filtered by a filter, the inside of the apparatus is lined with polytetrafluoroethylene or the like, and distillation or the like is performed under a condition that contamination is suppressed as much as possible.
In the resin composition of the present invention, when the use as a semiconductor material is considered, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosiveness. Wherein the amount present in the state of halide ion is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, further preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of the chlorine atom and the bromine atom or the chlorine ion and the bromine ion is preferably within the above range.
As a method for adjusting the halogen atom content, ion exchange treatment and the like are preferable.
In addition, from the viewpoint of reducing the amount of outgas generated from the cured product, the content of the component having a molecular weight of 1000 or less and different from the solvent contained in the resin composition is preferably 40 mass% or less with respect to the total solid content of the resin composition.
The molecular weight is preferably 800 or less, and more preferably 600 or less. The lower limit of the molecular weight is not particularly limited, and can be set to 50 or more, for example.
The content is preferably 30% by mass or less, and more preferably 10% by mass or less.
The lower limit of the content is not particularly limited, and may be set to 0 mass%.
As the container for containing the resin composition of the present invention, a conventionally known container can be used. In addition, as the storage container, a multilayer bottle having 6 kinds of 6 layers of resins constituting the inner wall of the container and a bottle having 6 kinds of resins and 7 layers of resins are preferably used for the purpose of suppressing the mixing of impurities into the raw material or the resin composition of the present invention. Examples of such a container include those described in Japanese patent application laid-open No. 2015-123351.
(resin composition)
The resin composition of the present invention contains a precursor of a cyclized resin.
When the glass transition temperature is measured under the following measurement condition 1, the glass transition temperature of at least 1 of 3 films having different thicknesses is 200 ℃ or higher.
Measurement condition 1:
the above resin composition was coated on a silicon substrate in a thickness of 5 μm, 10 μm or 20 μm, dried at 100℃for 5 minutes, and then heated at 180℃for 2 hours to obtain a cured product, and the glass transition temperature of the above cured product cooled to 25℃was measured by a differential scanning calorimeter.
According to the resin composition of the present invention, a cured product with a small amount of outgas generation can be obtained.
The mechanism for obtaining the above effects is not clear, but is presumed as follows.
The resin composition of the present invention has a glass transition temperature of 200 ℃ or higher when the glass transition temperature is measured under the above measurement condition 1, wherein at least 1 of 3 films having different thicknesses have a glass transition temperature.
Here, it is assumed that when the glass transition temperature is 200 ℃ or higher, the cyclizing rate of the cyclized resin in the cured product is high.
It is considered that the high cyclization ratio can suppress the occurrence of outgas due to cyclization or the like in the film after curing.
The heating for 2 hours in the above measurement condition 1 was performed under a nitrogen atmosphere.
The glass transition temperature was measured by the method described in examples.
The cyclizing rate of the cured product (cured product before glass transition temperature measurement) obtained under the measurement condition 1 is preferably 95% or more, more preferably 98% or more, and still more preferably 99% or more. The upper limit of the cyclization ratio is not particularly limited and may be 100%.
The cyclization ratio was measured by the method described above.
When the cyclization ratio is within the above range, movement (migration) of metal ions from the metal layer to the cured product with the uncycled portion as a permeation path can be suppressed, and a cured product excellent in adhesion to metal can be obtained.
The details of the components contained in the resin composition of the present invention, the characteristics of the resin composition, and the like are the same as those of the components in the resin composition used in the above-described method for producing a cured product of the present invention, the characteristics of the resin composition, and the like, and the preferable modes are also the same.
(cured product)
The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
The details of the cured product of the present invention are the same as those of the cured product obtained in the above-described method for producing a cured product of the present invention, and the preferable modes are also the same.
(laminate and method for producing laminate)
The laminate of the present invention is a structure having a plurality of layers formed from the cured product of the present invention.
The laminate of the present invention is a laminate comprising 2 or more layers of cured products, and may be a laminate comprising 3 or more layers.
Of the layers of the cured product of 2 or more layers contained in the laminate, at least 1 layer is a layer of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product accompanying the shrinkage, it is also preferable that all of the layers of the cured product contained in the laminate are layers of the cured product of the present invention.
That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes the step of repeating the method for producing a laminate of the present invention a plurality of times.
The laminate of the present invention comprises 2 or more layers formed of a cured product obtained by curing a resin composition containing a precursor of a cyclized resin, and at least 1 layer of the layers formed of the cured product is a layer formed of the cured product of the present invention.
Here, the mode in which the layers formed of the cured product included in the laminate are all layers formed of the cured product of the present invention is also one of preferred modes of the present invention.
The laminate of the present invention includes 2 or more layers of the cured product, and preferably includes a metal layer between any of the layers of the cured product. The metal layer is preferably formed by the metal layer forming step.
That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer formed of a cured product between the methods for producing a cured product that are carried out a plurality of times. The preferable mode of the metal layer forming step is as described above.
As the laminate, for example, a laminate having a layer structure in which at least 3 layers of a layer formed of a first cured product, a metal layer, and a layer formed of a second cured product are laminated in this order is preferable.
The layer formed of the first cured product and the layer formed of the second cured product are each preferably a layer formed of the cured product of the present invention. The resin composition of the present invention for forming a layer formed of the first cured product and the resin composition of the present invention for forming a layer formed of the second cured product may have the same composition or may have a composition different from each other. The metal layer in the laminate of the present invention can be preferably used as a metal wiring such as a rewiring layer.
< lamination Process >
The method for producing a laminate of the present invention preferably includes a lamination step.
The lamination step is a series of steps including performing at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, (d) a heating step, and a post-development exposure step again in this order on the surface of the pattern (resin layer) or the metal layer. The film forming step (a) and at least one of the heating step (d) and the post-development exposure step may be repeated. Further, the method may include (e) a metal layer forming step after at least one of the heating step and the post-development exposure step. The lamination step may obviously further include the above-described drying step or the like as appropriate.
When the lamination step is further performed after the lamination step, the surface activation treatment step may be further performed after the exposure step, after the heating step, or after the metal layer formation step. As the surface activation treatment, plasma treatment can be exemplified. Details of the surface activation treatment will be described later.
The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
For example, the resin layer is preferably a structure of 2 or more and 20 or less layers, more preferably a structure of 2 or more and 9 or less layers, such as a resin layer/metal layer/resin layer/metal layer.
The composition, shape, film thickness, etc. of the layers may be the same or different.
In the present invention, it is particularly preferable that after the metal layer is provided, the cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer. Specifically, the method includes a method in which (a) the film forming step, (b) the exposure step, (c) the developing step, (d) at least one of the heating step and the post-developing exposure step, and (e) the metal layer forming step are repeated in this order, or a method in which (a) the film forming step, (d) at least one of the heating step and the post-developing exposure step, and (e) the metal layer forming step are repeated in this order. The resin composition layer (resin layer) and the metal layer of the present invention can be alternately laminated by alternately performing the lamination step of laminating the resin composition layer (resin layer) and the metal layer formation step of the present invention.
(surface activation treatment Process)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface-activating at least a part of the metal layer and the resin composition layer.
The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after the surface activation treatment step is performed on the resin composition layer after the development step (preferably after at least one of the heating step and the post-development exposure step).
The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the resin composition layer after exposure, or may be performed on at least a part of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a part of the metal layer, and preferably, a part or the whole of the region of the metal layer where the resin composition layer is formed is surface-activated. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface thereof can be improved.
Further, it is also preferable to perform a surface activation treatment on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, adhesion with the metal layer and the resin layer provided on the surface subjected to the surface activation treatment can be improved. In particular, in the case of performing negative development or the like, when the resin composition layer is cured, the resin composition layer is less likely to be damaged by the surface treatment, and adhesion is easily improved.
The surface activation treatment may be specifically plasma treatment, corona discharge treatment, CF-based treatment, or the like from various source gases (oxygen, hydrogen, argon, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, or the like) 4 /O 2 、NF 3 /O 2 、SF 6 、NF 3 、NF 3 /O 2 The etching treatment, the surface treatment by Ultraviolet (UV) ozone method, the treatment of immersing in an aqueous hydrochloric acid solution to remove an oxide film and then immersing in an organic surface treating agent containing a compound having at least 1 of an amino group and a thiol group, and the mechanical roughening treatment using a brush are selected, and plasma treatment is preferable, and oxygen plasma treatment using oxygen as a source gas is particularly preferable. In the case of corona discharge treatment, the energy is preferably 500 to 200,000J/m 2 More preferably 1000 to 100,000J/m 2 Most preferably from 10,000 to 50,000J/m 2 。
(semiconductor device and method for manufacturing the same)
The present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention.
The present invention also discloses a method for manufacturing a semiconductor device including the method for manufacturing a cured product of the present invention or the method for manufacturing a laminate of the present invention.
As a specific example of a semiconductor device in which the resin composition of the present invention is used for forming an interlayer insulating film for a re-wiring layer, reference is made to the descriptions in paragraphs 0213 to 0218 and the description in fig. 1 of japanese patent application laid-open publication 2016-027357, which are incorporated herein by reference.
Examples
The present invention will be described in further detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment order, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass references.
(Synthesis example)
< Synthesis of polyimide precursor resin (SA-1)
23.7g (80.5 mmol) of 4,4' -biphenyltetracarboxylic dianhydride, 18.1g (139 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 28.2g (357 mmol) of pyridine and 80g of diglyme ether were mixed and stirred at 25 ℃. Then, a solution obtained by dissolving 1.72g (24.1 mmol) of pyrrolidine in 10g of diglyme was added dropwise over 30 minutes, followed by stirring at 60℃for 4 hours and cooling to 25 ℃. Then, after the reaction solution was cooled to-10 ℃, 20.1g (167 mmol) of thionyl chloride was added dropwise over 90 minutes, followed by stirring for 2 hours. Then, a solution of 23.2g (72.3 mmol) of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl dissolved in 100mL of NMP was added dropwise over 1 hour, followed by stirring for 2 hours. Next, 11.6g (256 mmol) of ethanol was added, the mixture was stirred for 2 hours, 50mL of tetrahydrofuran was added, the polyimide precursor resin was precipitated in 3 liters of water, and the water-polyimide precursor resin mixture was stirred at 500rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again, and the obtained polyimide precursor resin was dried at 45 ℃ under reduced pressure for 24 hours. Next, the dried polyimide precursor resin was dissolved in 300mL of tetrahydrofuran, 50g of ion exchange resin was added, and after stirring for 6 hours, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and dried at 45℃for 2 days, thereby obtaining a polyimide precursor (SA-1). The weight average molecular weight of the obtained polyimide precursor SA-1 was 22,900 and the number average molecular weight was 9100.
The structure of SA-1 is assumed to be represented by the following formula (SA-1).
[ chemical formula 61]
< Synthesis of polyimide precursor resins (SA-2 to SA-7) ]
SA-2 to SA-7 were synthesized in the same manner as SA-1 except that the types of amines (pyrrolidine in SA-1 synthesis) and alcohols (2-hydroxyethyl methacrylate in SA-1 synthesis) and the molar ratios of these were changed as described in the following tables, and carboxylic anhydride (4, 4' -biphenyltetracarboxylic dianhydride in SA-1 synthesis) and diamine (4, 4' -diamino-2, 2' -bis (trifluoromethyl) biphenyl in SA-1 synthesis) were appropriately changed.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of these resins are shown in the columns of Mw and Mn, respectively, of the following tables.
The structures of SA-2 to SA-7 are assumed to be represented by the following formulas (SA-2) to (SA-7), respectively. In the following formula, the brackets indicating the repeating units indicate the molar ratio of each repeating unit.
TABLE 1
[ chemical formula 62]
[ chemical formula 63]
< Synthesis of polyamideimide precursor resin (SA-8)
14.8g (47.6 mmol) of 4,4' -biphenyltetracarboxylic dianhydride, 10.68g (81.9 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 16.7g (210 mmol) of pyridine and 60g of diglyme were mixed and stirred at 25 ℃. Then, a solution obtained by dissolving 1.02g (14.3 mmol) of pyrrolidine in 10g of diglyme was added dropwise over 30 minutes, followed by stirring at 60℃for 4 hours and cooling to 25 ℃. Next, after the reaction solution was cooled to-10 ℃, 11.9g (99 mmol) of thionyl chloride was added dropwise over 90 minutes, followed by stirring for 2 hours. Next, 7.10g (23.8 mmol) of 4,4' -oxybenzoyl chloride was added thereto and stirred for 30 minutes. Subsequently, a solution of 25.0g (57 mmol) of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl dissolved in 100mL of NMP was added dropwise over 1 hour, followed by stirring for 2 hours. Subsequently, 9.0g (195 mmol) of ethanol was added, the mixture was stirred for 2 hours, 50mL of tetrahydrofuran was added, the polyimide precursor resin was precipitated in 3 liters of water, and the water-polyimide precursor resin mixture was stirred at 500rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again, and the obtained polyimide precursor resin was dried at 45 ℃ under reduced pressure for 24 hours. Next, the dried polyimide precursor resin was dissolved in 300mL of tetrahydrofuran, 50g of ion exchange resin was added, and after stirring for 6 hours, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500rpm for 15 minutes. The polyimide precursor resin was obtained by filtration and dried at 45℃for 2 days, whereby a polyimide precursor (SA-8) was obtained. The weight average molecular weight of the obtained polyimide precursor SA-8 was 24,200, and the number average molecular weight was 10,100. The structure of SA-8 is assumed to be represented by the following formula (SA-8). In the following formula, the brackets indicating the repeating units indicate the molar ratio of each repeating unit.
[ chemical formula 64]
< Synthesis of HA-1 >
In a flask, 34.53g (164 mmol) of trimellitic anhydride and 150g of tetrahydrofuran were weighed, and stirred and dissolved at-10℃to 0 ℃. Subsequently, a solution of 25.0g (78.1 mmol) of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl and 13.6g (178.1 mmol) of pyridine in 150g of tetrahydrofuran was added dropwise to the flask over 2 hours, and the mixture was stirred for 30 minutes. Then, the internal temperature of the flask was raised to 20 to 25℃and stirred for 2 hours, and the reaction solution was diluted in 700mL of ethyl acetate and transferred to a separating funnel. The ethyl acetate solution was washed with 300mL of water 2 times, 300mL of saturated sodium bicarbonate water 2 times, 300mL of diluted hydrochloric acid 2 times, 500mL of saturated brine 1 time, dried over sodium sulfate, and about 90% of the solvent was removed by an evaporator, whereby an ethyl acetate solution was obtained. Then, the solution was crystallized in hexane 1L, stirred for 30 minutes, filtered, and dried in vacuo, whereby 50g of HA-1 was obtained. HA-1 is a compound of the following structure.
By passing through 1 H-NMR was confirmed to be HA-1.
[ chemical formula 65]
< Synthesis of SA-9 >
22.8g (34 mmol) of HA-1 (the above-mentioned synthetic product), 9.06g (69.5 mmol) of 2-hydroxyethyl methacrylate, 0.03g of hydroquinone, 112.0g (151 mmol) of pyridine and 80g of diglyme were mixed and stirred at 25 ℃. Then, the mixture was stirred at 60℃for 4 hours and cooled to 25 ℃. Then, after the reaction solution was cooled to-10 ℃, 8.51g (71 mmol) of thionyl chloride was added dropwise over 90 minutes, followed by stirring for 2 hours. Then, a solution of 9.27g (28.9 mmol) of 4,4 '-diamino-2, 2' -bis (trifluoromethyl) biphenyl dissolved in 100mL of NMP was added dropwise over 1 hour, followed by stirring for 2 hours. Next, 11.6g (256 mmol) of ethanol was added, the mixture was stirred for 2 hours, 50mL of tetrahydrofuran was added, the polyimide precursor resin was precipitated in 3 liters of water, and the water-polyimide precursor resin mixture was stirred at 500rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again, and the obtained polyimide precursor resin was dried at 45 ℃ under reduced pressure for 24 hours. Next, the dried polyimide precursor resin was dissolved in 300mL of tetrahydrofuran, 50g of ion exchange resin was added, and after stirring for 6 hours, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500rpm for 15 minutes. The polyimide precursor resin was obtained by filtration and dried at 45℃for 2 days, whereby a polyamideimide precursor (SA-9) was obtained. The weight average molecular weight of the obtained polyamideimide precursor SA-9 was 26,100 and the number average molecular weight was 11,300.
The structure of SA-9 is assumed to be represented by the following formula (SA-9).
[ chemical formula 66]
< Synthesis of A-1 >
[ Synthesis of polyimide precursor from 4,4 '-oxydiphthalic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-1: polyimide precursor having radical polymerizable group) ]
In a dry reactor equipped with a stirrer, condenser and a flat-bottom joint with an internal thermometer, 20.0g (65 mmol) of oxydiphthalic dianhydride was suspended in 140mL of diglyme while removing moisture. 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 0.05g of pure water and 10.7g (135 mmol) of pyridine were continuously added, and the mixture was stirred at 60℃for 18 hours. Next, after cooling the mixture to-20 ℃, 16.1g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Subsequently, the mixture was warmed to room temperature and stirred for 2 hours, and then 9.7g (123 mmol) of pyridine and 25mL of N-methylpyrrolidone (NMP) were added thereto to obtain a transparent solution. Next, a solution obtained by dissolving 11.8g (58.7 mmol) of 4,4' -diaminodiphenyl ether in 100mL of NMP was added dropwise over 1 hour. Next, 5.6g (17.5 mmol) of methanol and 0.05g of 3, 5-di-t-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred in 4 liters of water for 30 minutes again and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ℃ under reduced pressure for 3 days to obtain a polyimide precursor (a-1). The weight average molecular weight of the obtained polyimide precursor A-1 was 22,100, and the number average molecular weight was 9,400.
< Synthesis of A-2 >
[ A-2: synthesis of polyimide precursor from 4,4 '-oxydiphthalic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-2: polyimide precursor having radical polymerizable group)
155.1g of 4,4' -oxybisphthalic anhydride (ODPA) was placed in a separate flask, and 134.0g of 2-hydroxyethyl methacrylate (HEMA) and 400ml of gamma-butyrolactone were added. 79.1g of pyridine was added while stirring at room temperature, whereby a reaction mixture was obtained. After the completion of the heat generation by the reaction, the reaction mixture was cooled to room temperature and allowed to stand for 16 hours.
Then, a solution of 206.3g of Dicyclohexylcarbodiimide (DCC) dissolved in 180ml of γ -butyrolactone was added to the reaction mixture over 40 minutes while stirring under ice-cooling. Subsequently, 93.0g of 4,4' -diaminodiphenyl ether was added to a suspension of 350ml of gamma-butyrolactone with stirring over a period of 60 minutes. After stirring at room temperature for 2 hours, 30ml of ethanol was added thereto and stirred for 1 hour. Thereafter, 400ml of gamma-butyrolactone was added. The precipitate formed in the reaction mixture was obtained by filtration, and a reaction solution was obtained.
The obtained reaction solution was added to 3 liters of ethanol, and a precipitate composed of a crude polymer was formed. The crude polymer thus produced was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran, whereby a crude polymer solution was obtained. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was collected by filtration and then subjected to vacuum drying, whereby polymer A-2 was obtained in the form of a powder. The weight average molecular weight (Mw) of this polymer A-2 was measured, and found to be 24,000.
< examples and comparative examples >
In each example, the components described in the following table were mixed, respectively, to thereby obtain each resin composition. In the comparative example, the ingredients described in the following table were mixed to obtain a composition for comparison.
Specifically, the content of each component described in the table is set to the amount (parts by mass) described in the column "addition amount" of each column in the table.
The obtained resin composition and comparative composition were subjected to pressure filtration using a polytetrafluoroethylene filter having a pore width of 0.5. Mu.m.
In the table, "-" indicates that the composition does not contain any corresponding components.
TABLE 2
TABLE 3
[ resin ]
SA-1 to SA-9: SA-1 to SA-9 synthesized as above
A-1 to A-2: a-1 to A-2 synthesized above
[ polymerizable Compound (trade name in each case) ]
SR-209: SR-209 (Sartomer Company, manufactured by Inc)
A-DPH (Shin-Nakamura Chemical Co., ltd., dipivalol hexaacrylate)
A-DCP (Shin-Nakamura Chemical Co., ltd., tricyclodecane dimethanol diacrylate)
[ polymerization initiators (all trade names) ]
C-1: IRGACURE OXE 01 (manufactured by BASF corporation)
C-2: IRGACURE OXE 02 (manufactured by BASF corporation)
C-3: compounds of the structure
[ chemical formula 67]
C-4: IRGACURE 784 (manufactured by BASF corporation)
[ migration inhibitor ]
E-1 to E-6: compounds of the structure
[ chemical formula 68]
[ Metal adhesion improver ]
F-1 to F-3: compounds of the structure
[ chemical formula 69]
[ polymerization inhibitor ]
G-1:1, 4-benzoquinone
G-2: 4-methoxyphenol
G-3:1, 4-dihydroxybenzene
G-4: compounds of the structure
[ chemical formula 70]
[ other additives ]
H-1: n-phenyl diethanolamine (Tokyo ChemicalIndustry Co., ltd.)
H-2: n-hydroxyphthalimide (Tokyo ChemicalIndustry Co., ltd.)
[ solvent ]
DMSO: dimethyl sulfoxide
GBL: gamma-butyrolactone
NMP: n-methylpyrrolidone
MDPA: 3-methoxy-N, N-dimethylpropionamide
In the tables, "DMSO/GBL" means that DMSO is used: gbl=80: 20 (mass ratio) of DMSO and GBL.
[ developer solution ]
I-1: cyclohexanone
I-2: cyclohexanone solution of 5 mass% of dimethylcyclohexylamine
[ flushing liquid ]
J-1: PGMEA (propylene glycol monomethyl ether acetate)
J-2: PGMEA solution of 10% by mass of dimethylcyclohexylamine
< evaluation >
[ evaluation of copper adhesion ]
The respective resin compositions and the comparative compositions after filtration were applied to copper substrates in layers by spin coating, thereby forming curable resin composition layers. The copper substrate to which the obtained curable resin composition layer was applied was dried on a hot plate at l00℃for 5 minutes, thereby producing a uniform curable resin composition layer having a thickness of 20. Mu.m on the copper substrate. Using a stepper (Nikon NSR 2005 i9C) at 500mJ/cm 2 After exposing the curable resin composition layer on the copper substrate using a 100 μm square pattern forming photomask, the curable resin composition layer was developed with a developing solution described in the column of "developing solution" for 60 seconds, and rinsed with a rinsing solution described in the column of "rinsing solution" for 30 seconds, whereby a 100 μm square resin layer was obtained. Further, the temperature was raised at the temperature rise rate described in the column of "temperature rise rate" in the table under a nitrogen atmosphere, and after the temperature reached the temperature described in the column of "temperature" in the table of "curing condition", the temperature was maintained for 2 hours, whereby the resin film 2 was obtained.
The glass transition temperature of the resin film 2 was the same as that of the cured product used for the evaluation of the deaeration property.
Shear force was measured on the 100 μm square resin film 2 on the copper substrate using an adhesion tester (CondorSigma, manufactured by XYZTEC Co.) at 25℃under an environment of 65% Relative Humidity (RH). The greater the shear force, the greater the adhesion, and thus the preferred result. The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column "adhesion" in the table.
Evaluation criterion-
A: the shearing force exceeds 30gf.
B: the shearing force exceeds 25gf and is less than 30gf.
C: the shearing force exceeds 20gf and is less than 25 gf.
D: the shearing force is 20gf or less.
Further, 1gf was 0.00980665N.
[ evaluation of degassing ]
In each of examples and comparative examples, a resin composition layer was formed by applying a resin composition or a composition for comparison to a silicon wafer by spin coating. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100℃for 5 minutes, and a uniform resin composition layer of about 15 μm thickness was obtained on the silicon wafer. Using a stepper (Nikon NSR 2005 i9C) at 500mJ/cm 2 The entire surface of the obtained resin composition layer was subjected to i-ray exposure. After the exposure, the film was developed with the developer described in the column "developer" in the table for 60 seconds, and rinsed with the rinse solution described in the column "rinse solution" in the table for 30 seconds.
The resin composition layer (resin layer) after the flushing was heated in a nitrogen atmosphere at a temperature rise rate indicated in the column of "temperature rise rate" in the table, and after reaching a temperature indicated in the column of "temperature" of "curing condition" in the table, it was heated for 2 hours. The cured resin layer (cured product) was immersed in a 4.9 mass% aqueous hydrofluoric acid solution, and the cured product was peeled from the silicon wafer. 1 to 5mg of the peeled film was weighed on an aluminum plate, and TG-DTA2500 was manufactured by NETZSCH Japan k.k, and the mass reduction rate was measured under the following conditions.
Measurement conditions-
The temperature conditions were changed in the order of (1) to (3) below under a nitrogen atmosphere, the mass before (mass a) and the mass after (mass B) were measured, and the mass reduction rate was calculated by the following formula.
(1) Heating from 25 ℃ to 270 ℃ at a speed of 10 ℃ per minute
(2) Maintaining at 270 ℃ for 30 minutes
(3) Cooling to below 25deg.C
Mass reduction rate (%) = (1-mass B/mass a) ×100
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column "outgassing" in the table. It can be said that the smaller the mass reduction ratio is, the more excellent the outgassing is.
Evaluation criterion-
A: the mass reduction rate is less than 2%.
B: the mass reduction rate is 2% or more and less than 4%.
C: the mass reduction rate is 4% or more and less than 7%.
D: the mass reduction rate is 7% or more.
[ measurement of imidization Rate ]
The cyclized ratio (imidization ratio) of the cured product obtained in the above evaluation of deaeration was measured and is shown in the column "imidization ratio" in the table.
The imidization ratio was calculated by the following method.
As to the resin film 2, 1377cm, which is the absorption peak derived from the imide structure, was obtained -1 The near peak intensity P1 was measured again by heat-treating the resin film 2 at 350℃for 1 hour and then measuring the infrared absorption spectrum, thereby obtaining 1377cm -1 A nearby peak intensity P2.
Using the obtained peak intensities P1 and P2, the imidization ratio of the polyimide was calculated according to the following formula.
Imidization ratio (%) = (peak intensity P1/peak intensity P2) ×100
[ measurement of glass transition temperature (1) ]
The glass transition temperature of the cured product (cured product before heating in an aluminum pan) obtained in the above evaluation of the degassing property was measured under the following measurement conditions.
< measurement condition >
A differential scanning calorimeter was used to prepare a differential scanning calorimetric curve by changing the temperature conditions of the cured product in the following order (1) to (4) under a nitrogen atmosphere, and the temperature at the intersection point of a straight line extending the low-temperature side base line of the differential scanning calorimetric curve to the high-temperature side and a tangential line drawn at a point where the gradient of the curve at the stage-like change portion of the glass transition becomes maximum was measured as the glass transition temperature.
(1) Heating from 25 ℃ to 300 ℃ at a speed of 10 ℃/min
(2) Cooling from 300 ℃ to 25 DEG C
(3) Heating from 25 ℃ to 500 ℃ at a speed of 10 ℃/min
(4) Cooling from 500 ℃ to 25 DEG C
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column "glass transition temperature (1)" in the table.
Evaluation criterion-
A: the glass transition temperature of the cured product is 250 ℃ or higher.
B: the glass transition temperature of the cured product is less than 250 ℃ and more than 200 ℃.
C: the glass transition temperature of the cured product is less than 200 ℃ and 190 ℃ or higher.
D: the glass transition temperature of the cured product is less than 190 ℃.
[ measurement of glass transition temperature (2) ]
The resin compositions and comparative compositions used in the examples and comparative examples were applied to silicon wafers by spin coating to form resin composition layers having a total of 3 thicknesses of 5 μm, 10 μm and 20 μm, respectively. When coating with a film thickness of 20. Mu.m, the spin coating was performed with the rotation speed set to 2000 rpm. When the coating was performed at a film thickness of 10 μm, the solid content concentration of the composition was diluted to 29 mass% with the solvent (the solvent described in the table) contained in each composition, and the spin-coating was performed at a rotation speed of 1500 rpm. When the coating was performed at a film thickness of 5 μm, the solid content concentration of the composition was diluted to 29 mass% with the solvent (the solvent described in the table) contained in each composition, and the spin coating was performed at a rotation speed of 3000 rpm. The silicon wafer to which the obtained resin composition layer was applied was dried at 100 ℃ for 5 minutes on a heating plate, respectively, to thereby form a resin composition layer on the silicon wafer.
The resin composition layer was heated at a heating rate of 10 ℃/min under a nitrogen atmosphere to 180 ℃, and then the temperature was maintained for 2 hours, whereby a cured product was obtained.
The cured product was immersed in a 4.9 mass% aqueous hydrofluoric acid solution, and the cured product was peeled from the silicon wafer. For the obtained cured product, the glass transition temperature was measured according to the following measurement conditions.
< measurement condition >
A differential scanning calorimeter was used to prepare a differential scanning calorimetric curve by changing the temperature conditions of the cured product in the following order (1) to (4) under a nitrogen atmosphere, and the temperature at the intersection point of a straight line extending the low-temperature side base line of the differential scanning calorimetric curve to the high-temperature side and a tangential line drawn at a point where the gradient of the curve at the stage-like change portion of the glass transition becomes maximum was measured as the glass transition temperature.
(1) Heating from 25 ℃ to 300 ℃ at a speed of 10 ℃/min
(2) Cooling from 300 ℃ to 25 DEG C
(3) Heating from 25 ℃ to 500 ℃ at a speed of 10 ℃/min
(4) Cooling from 500 ℃ to 25 DEG C
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column "glass transition temperature (2)" in the table. In the example described as "-" in the column of "glass transition temperature (2)", the measurement of glass transition temperature (2) was not evaluated.
Evaluation criterion-
A: the minimum value of the glass transition temperature of the cured product of 3 thicknesses is 250 ℃ or higher.
B: the minimum value of the glass transition temperature of the cured product of 3 thickness is less than 250 ℃ and more than 200 ℃.
C: the minimum value of the glass transition temperature of the cured product of 3 thickness is less than 200 ℃ and more than 190 ℃.
D: the minimum value of the glass transition temperatures of the cured products with the 3 thicknesses is less than 190 ℃.
From the above results, it was found that the cured product obtained by the method for producing a cured product of the present invention and the cured product formed from the resin composition of the present invention can suppress the occurrence of outgas.
In the method for producing a cured product of comparative example, the glass transition temperature of the obtained cured product was less than 200℃and the glass transition temperature of the resin composition of comparative example 1 under measurement condition 1 was less than 200 ℃.
It was found that the amount of outgas generated from the cured product obtained by the method for producing a cured product according to comparative example 1 was large.
< example 101>
The resin composition used in example 1 was applied to the copper thin layer surface of the resin substrate having a copper thin layer formed thereon in a layer form by spin coating, dried at 100℃for 4 minutes to form a resin composition layer having a film thickness of 20. Mu.m, and then exposed to light by a stepper (manufactured by Nikon Corporation, NSR1505 i 6). Exposure was performed at 365nm wavelength through a mask (binary mask with a pattern of 1:1 lines and spaces, line width of 10 μm). After exposure, the mixture was heated at 100℃for 4 minutes. After the above heating, the layer was developed with cyclohexanone (I-1) for 2 minutes and rinsed with PGMEA (J-1) for 30 seconds, thereby obtaining a pattern of the layer.
Then, the temperature was raised at a temperature raising rate of 10 ℃/min in a nitrogen atmosphere, and after reaching 180 ℃, the temperature was maintained at 180 ℃ for 2 hours, thereby forming an interlayer insulating film for a rewiring layer. The interlayer insulating film for a rewiring layer is excellent in insulation properties.
Further, a semiconductor device was manufactured using these interlayer insulating films for a rewiring layer, and as a result, normal operation was confirmed.

Claims (24)

1. A method for producing a cured product, comprising:
a film forming step of forming a film by applying a resin composition containing a precursor of a cyclized resin to a substrate; and
A heating step of heating the film at a heating temperature of 180 ℃ or lower,
the glass transition temperature of the obtained cured product is 200 ℃ or higher.
2. The method for producing a cured product according to claim 1, wherein,
the heating temperature is below 170 ℃.
3. The method for producing a cured product according to claim 1 or 2, wherein,
the film after the heating step is a polyimide film containing polyimide, and the imidization rate of the polyimide is 90% or more.
4. The method for producing a cured product according to any one of claims 1 to 3, further comprising an exposure step of selectively exposing the film between the film forming step and the heating step.
5. The method for producing a cured product according to claim 4, further comprising a developing step of developing the film after exposure with a developing solution to form a pattern between the exposing step and the heating step.
6. The method for producing a cured product according to claim 5, wherein,
the developer contains an organic solvent.
7. The method for producing a cured product according to claim 5 or 6, wherein,
the developing step is a step of forming a negative pattern.
8. The method for producing a cured product according to any one of claims 5 to 7, wherein,
the developer contains a base.
9. The method for producing a cured product according to any one of claims 5 to 8, comprising a treatment step of bringing a treatment liquid containing a base into contact with the pattern between the development step and the heating step.
10. The method for producing a cured product according to any one of claim 1 to 9, wherein,
the resin composition includes a sensitizer.
11. The method for producing a cured product according to any one of claims 1 to 10, wherein,
the resin composition comprises a solvent and,
the content of the precursor of the cyclized resin is 70 mass% or more relative to the total solid content of the resin composition.
12. The method for producing a cured product according to any one of claims 1 to 11, wherein,
the resin composition comprises a polymerizable compound having a boiling point of 200 ℃ or higher at 1 atmosphere.
13. The method for producing a cured product according to claim 12, wherein,
the polymerizable compound having a boiling point of 200 ℃ or higher at 1 atmosphere is a compound having 3 or more (meth) acrylate groups.
14. The method for producing a cured product according to any one of claims 1 to 13, wherein,
the resin composition includes a polymerizable compound having an aliphatic ring structure.
15. The method for producing a cured product according to any one of claims 1 to 14, wherein,
the precursor of the cyclized resin is a resin having at least one of the repeating units represented by the following formula (2) and the repeating units represented by the following formula (PAI-2),
in the formula (2), A 1 A is a 2 Each independently represents an oxygen atom or-NR z -，R 111 Represents a 2-valent organic group, R 115 Represents a 4-valent organic group, R 113 R is R 114 Each independently represents a hydrogen atom or a 1-valent organic group, R z Represents a hydrogen atom or a 1-valent organic group,
in the formula (PAI-2), R 117 Represents a 3-valent organic group, R 111 Represents A2-valent organic group, A2 represents an oxygen atom or-NR z R113 represents a hydrogen atom or a 1-valent organic group, R z Represents a hydrogen atom or a 1-valent organic group.
16. The method for producing a cured product according to claim 15, wherein,
r in the formula (2) 115 The group represented by any one of the following formulas (X1-1) to (X1-3) or a group having 1 or more aliphatic ring structures,
r in the formula (PAI-2) 117 The group represented by any one of the following formulas (X2-1) to (X2-3) or a group having 1 or more aliphatic ring structures,
in the formula (X1-1), R represents a substituent, n1 represents an integer of 0 to 2, each represents a bonding site with other structure,
in the formula (X1-2), R independently represents a substituent, m1 independently represents an integer of 0 to 3, each represents a bonding site with other structure,
in the formula (X1-3), R independently represents a substituent, m1 independently represents an integer of 0 to 2, and L 1 representation-CR C 2 -or-S (=o) 2 -or-O-, R C Represents a 1-valent organic group, each represents a bonding site to another structure,
in the formula (X2-1), R represents a substituent, n2 represents an integer of 0 to 2, each represents a bonding site with other structure,
in the formula (X2-2), R independently represents a substituent, m2 represents an integer of 0 to 3, m3 represents an integer of 0 to 4, each represents a bonding site with other structure,
In the formula (X2-3), R independently represents a substituent, m2 represents an integer of 0 to 2, m3 represents an integer of 0 to 3, L 2 representation-CR C 2 -、-S(＝O) 2 -or-O-, R C Represents a 1-valent organic group, and each represents a bonding site to another structure.
17. The method for producing a cured product according to claim 15 or 16, wherein,
r in the formula (2) 111 The group represented by any one of the following formulas (W1-1) to (W1-5) or a group having 1 or more aliphatic ring structures,
r in the formula (PAI-2) 111 The group represented by any one of the following formulas (W1-1) to (W1-3) or a group having 1 or more aliphatic ring structures,
in the formula (W1-1), R represents a substituent, n1 represents an integer of 0 to 4, each represents a bonding site with other structure,
in the formula (W1-2), R independently represents a substituent, m4 independently represents an integer of 0 to 4, each represents a bonding site with other structure,
in the formula (W1-3), R independently represents a substituent, m4 independently represents an integer of 0 to 3, and L 3 representation-CR C 2 -or-S (=o) 2 -，R C Represents a 1-valent organic group, each represents a bonding site to another structure,
in the formula (W1-4), R independently represents a substituent, n3 represents an integer of 0 to 6, each represents a bonding site with other structure,
In the formula (W1-5), R independently represents a substituent, n4 independently represents an integer of 0 to 3, and X 1 X is X 2 Each independently represents an oxygen atom, -S (=O) 2 or-CR C2- RC independently represents a hydrogen atom or a 1-valent organic group, and represents a bonding site to another structure.
18. The method for producing a cured product according to any one of claims 15 to 17, wherein,
when the precursor of the cyclized resin does not contain the repeating unit represented by the formula (PAI-2), the following condition 1 is satisfied,
when the precursor of the cyclized resin does not contain the repeating unit represented by formula (2), the following condition 2 is satisfied,
when the precursor of the cyclized resin comprises a repeating unit represented by formula (2) and a repeating unit represented by formula (PAI-2), at least one of the following conditions 1 and 2 is satisfied,
condition 1: the precursor of the cyclized resin comprises-A in the formula (2) 2 -R 113 -A 1 -R 114 At least one of them is a repeating unit of a group represented by the following formula (3-1),
condition 2: the precursor of the cyclized resin comprises-A in the formula (PAI-2) 2 -R 113 Is a repeating unit of a group represented by the following formula (3-1),
in the formula (3-1), Z 1 Z is as follows 2 Each independently represents an organic group, Z 1 And Z is 2 Optionally bonded to form a ring structure, represents a bonding site to other structures.
19. A method for producing a laminate, comprising repeating the method for producing a cured product according to any one of claims 1 to 18 a plurality of times.
20. A manufacturing method of a semiconductor device, comprising the manufacturing method of the cured product according to any one of claims 1 to 18 or the manufacturing method of the laminate according to claim 19.
21. A resin composition comprising a precursor of a cyclized resin,
when the glass transition temperature is measured under the following measurement condition 1, the glass transition temperature of at least 1 of 3 films having different thicknesses is 200 ℃ or higher,
measurement condition 1:
the resin composition was coated on a silicon substrate at a thickness of 5 μm, 10 μm or 20 μm, respectively, and after drying at 100℃for 5 minutes, a cured product was obtained by heating at 180℃for 2 hours, and the glass transition temperature of the cured product cooled to 25℃was measured by a differential scanning calorimeter.
22. A cured product obtained by curing the resin composition according to claim 21.
23. A laminate comprising 2 or more layers formed from a cured product obtained by curing a resin composition containing a precursor of a cyclized resin,
At least one of the layers formed of the cured product of claim 22.
24. A semiconductor device comprising the cured product of claim 22 or the laminate of claim 23.
CN202280053079.7A 2021-07-30 2022-06-30 Method for producing cured product, method for producing laminate, method for producing semiconductor device, resin composition, cured product, laminate, and semiconductor device Pending CN117751326A (en)

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