TW202323370A - Photosensitive composition, dry film, cured product, and electronic component - Google Patents

Abstract

The present invention addresses the problem of providing a photosensitive composition having low dielectric properties and excellent development contrast. This problem is solved by a photosensitive composition containing a polyphenylene ether A, a polyphenylene ether B, a radically polymerizable compound, and a photoradical generator, the polyphenylene ethers A, B each being obtained from raw material phenols including a phenol satisfying a condition 1 and a phenol satisfying a condition 2, the polyphenylene ether A having a weight-average molecular weight of more than 40,000 and less than or equal to 200,000 and containing less than 20 mol% of the phenol satisfying the condition 2 relative to all of the raw material phenols, and the polyphenylene ether B containing 20 mol% or more of the phenol satisfying the condition 2 relative to all of the raw material phenols. (Condition 1) Having hydrogen atoms at the ortho and para positions (Condition 2) Having a hydrogen atom at the para position and having a functional group containing an unsaturated carbon bond.

Description

Photosensitive composition, dry film, cured product and electronic parts

The present invention relates to a photosensitive composition containing polyphenylene ether, a dry film, a cured product and an electronic part.

In electronic components such as semiconductor devices, photolithography is often used to form patterns of insulating layers, protective films, and conductive layers.

The photolithography method is to form a layer composed of a photosensitive composition on a substrate such as a silicon wafer or a copper-clad laminate. After the light is irradiated (exposed) to a prescribed pattern, the unexposed part or the exposed part is dissolved and removed with a developing solution. Either of them is a method of forming a pattern. This photolithography method has: the method of dissolving the exposed part in the developer, that is, the positive type; and the method of dissolving the unexposed part in the developer (the exposed part is insoluble in the developer), that is, the negative type.

Considering the difference in the development steps, for example, in order to form a high-resolution pattern in the negative type, the photosensitive composition used is required to have both the resistance to dissolution of the exposed part in the developing solution and the excellent dissolution of the unexposed part in the developing solution In other words, it is required that the development speed difference (development contrast) between the exposed part and the unexposed part is large.

On the other hand, in insulating materials for electronic parts, from the viewpoint of suppressing transmission loss for high frequency band signals, it is considered to reduce dielectric properties such as relative permittivity (Dk) and dielectric tangent (Df). For example, Patent Documents 1 and 2 have disclosed that solder resist as a permanent protective film of a printed wiring board is a useful negative photosensitive resin composition for lowering the dielectric tangent. [Prior Art Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2017-15890 Patent Document 2: Japanese Patent Laid-Open No. 2017-68242

[Problem to be Solved by the Invention]

However, in the photosensitive resin compositions of Patent Documents 1 and 2, as composition components, even if a hydrophilic group such as a carboxyl group for imparting developability or a (meth)acrylate group for imparting photopolymerization To reduce the dielectric properties, but there is still a limit.

The object of the present invention is to provide a photosensitive composition having low dielectric properties and excellent development contrast. [Means to solve the problem]

The inventors of the present invention focused on polyphenylene ether having a branched structure soluble in an organic solvent, and conducted intensive studies using photolithography using the organic solvent as a developing solution. As a result, the inventors of the present invention found that by combining two kinds of polyphenylene ethers obtained from specific raw material phenols and a compound introduced into the polyphenylene ethers to radically polymerize unsaturated carbon bonds, the photosensitive The property composition can be advantageous in solving the above-mentioned problems, thereby completing the present invention. That is, the present invention is as follows.

The present invention is a photosensitive composition, which includes: polyphenylene ether A, polyphenylene ether B, a compound having a functional group capable of radical polymerization with an unsaturated carbon bond, and a photoradical generator, The polyphenylene ether A and the polyphenylene ether B are obtained from raw material phenols including phenols satisfying at least the following condition 1 and phenols satisfying at least the following condition 2, respectively, The polyphenylene ether A-based weight average molecular weight is more than 40,000 and not more than 200,000, and the content of phenols satisfying condition 2 is less than 20 mol% with respect to the entire raw material phenols at the time of synthesis, The content of the polyphenylene ether B-based phenols satisfying Condition 2 is 20 mol% or more relative to the entire raw material phenols at the time of synthesis. (Condition 1) Has hydrogen atoms in the ortho and para positions (Condition 2) Has a hydrogen atom at the para position and has a functional group containing an unsaturated carbon bond

The polyphenylene ether B-based weight average molecular weight is preferably not less than 5,000 and not more than 40,000. The content ratio of the aforementioned polyphenylene ether A to the aforementioned polyphenylene ether B (polyphenylene ether A: polyphenylene ether B) is based on a mass ratio, preferably 25:75-75:25. The aforementioned functional groups capable of radical polymerization with unsaturated carbon bonds are preferably thiol groups and/or allyl groups.

The present invention may be a dry film having a resin layer composed of the aforementioned photosensitive composition.

The present invention may be a cured product of the aforementioned photosensitive composition or the aforementioned resin layer.

The present invention may be an electronic component having the aforementioned cured product. [Effect of the invention]

According to the present invention, it is possible to provide a photosensitive composition with low dielectric properties and excellent development contrast.

The curable composition of this embodiment is a photosensitive composition used in photolithography.

Hereinafter, the photosensitive composition may only be referred to as "curable composition". In addition, in this specification, "resin composition" can be used in the meaning of "curable composition".

When there are isomers in the illustrated compounds, all the isomers that may exist may be used in the present invention unless specifically excluded.

In the present invention, "unsaturated carbon bond" means an ethylenic or acetylene carbon-carbon multiple bond (double bond or triple bond) unless specifically excluded.

In the present invention, the functional group having an unsaturated carbon bond is not particularly limited, and examples include alkenyl (for example, vinyl, allyl), alkynyl (for example, ethynyl), or (meth)acrylic As the acyl group, vinyl, allyl, and (meth)acryl can be selected from the viewpoint of excellent curability, and among them, allyl is preferable from the viewpoint of excellent low dielectric properties. In addition, these functional groups having an unsaturated carbon bond can have a carbon number of, for example, 15 or less, 10 or less, 8 or less, 5 or less, 3 or less, and the like.

In the present invention, phenols that can be used as raw materials for polyphenylene ether (PPE) are collectively referred to as "raw material phenols" that can serve as constituent units of polyphenylene ether.

In the present invention, when describing raw material phenols, when "ortho position", "para position" and the like are indicated, unless otherwise specifically excluded, the position of the phenolic hydroxyl group is taken as the reference (standard position).

In the present invention, when only "ortho position" and the like are indicated, "at least one of the ortho position" and the like are indicated. Therefore, as long as there is no particular contradiction, when only "neighbor" is used, it can be interpreted as indicating either one of the neighbors, or both of the neighbors.

In the present invention, the number average molecular weight (Mn) and weight average molecular weight (Mw) of polyphenylene ether are obtained by gel permeation chromatography (GPC). In GPC, Shodex K-805L was used as a column, the column temperature was set to 40°C, the flow rate was set to 1mL/min, the eluent was set to chloroform, and the standard substance was set to polystyrene.

In this specification, monovalent phenols are mainly shown as raw material phenols, but polyvalent phenols can be used as raw material phenols in the range which does not inhibit the effect of this invention.

In this specification, when an upper limit and a lower limit of a numerical range are described separately, it is assumed that substantially all combinations of each lower limit and each upper limit are described within the range where no contradiction arises.

＜＜＜＜Components of hardening composition＞＞＞＞＞ The curable composition includes: polyphenylene ether A, polyphenylene ether B, a compound having a functional group capable of radical polymerization with an unsaturated carbon bond, and a photoradical generator. In addition, the curable composition may contain other components as needed. Hereinafter, each component is demonstrated.

＜＜＜＜Polyphenylene ether A, B＞＞＞＞ The polyphenylene ethers A and B contained in the curable composition of the present invention are respectively obtained from raw material phenols including phenols satisfying at least the following condition 1 and phenols satisfying at least the following condition 2. Specifically, as the phenols satisfying at least the following condition 1, phenols satisfying the condition 1 but not satisfying the condition 2 or satisfying the conditions 1 and 2 are exemplified; as the phenols satisfying at least the following condition 2 , exemplified are phenols satisfying condition 2 but not satisfying condition 1, or phenols satisfying condition 1 and condition 2. (Condition 1) Has hydrogen atoms in the ortho and para positions (Condition 2) Has a hydrogen atom at the para position and has a functional group containing an unsaturated carbon bond

＜＜＜Raw material phenol (type)＞＞＞ ＜＜Phenols that satisfy condition 1＞＞ Phenols satisfying condition 1 have a hydrogen atom at the ortho-position, so when oxidatively polymerized with phenols, ether bonds can be formed not only at the home and para-positions, but also at the ortho-position, so this phenol is used as a raw material phenol Polyphenylene ether may form a branched structure.

Specifically, a polyphenylene ether obtained from a phenol satisfying condition 1 has a part of its structure branched at least at three positions of the ortho-position and the para-position through the benzene ring bonded via ether.

As mentioned above, polyphenylene ether having a branched structure in its skeleton is called branched polyphenylene ether. With the branched polyphenylene ether, excellent solubility in organic solvents can be obtained.

Phenols satisfying condition 1 include phenol, o-cresol, m-cresol, o-ethylphenol, m-ethylphenol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, -Xylenol, o-tert-butylphenol, m-tert-butylphenol, o-phenylphenol, m-phenylphenol, 2-dodecylphenol, etc., may use only one type, or may use two more than one species.

＜＜Phenols that satisfy condition 2＞＞ Phenols satisfying condition 2 have functional groups containing unsaturated carbon bonds, and therefore polyphenylene ethers obtained by using such phenols as raw material phenols have functional groups containing ethylenic or acetylenic carbon-carbon multiple bonds.

Specifically, a polyphenylene ether obtained from a phenol satisfying condition 2 has a functional group including an unsaturated carbon bond at least in either the inter-position or the two ortho-positions of the benzene ring as part of its structure.

As mentioned above, a polyphenylene ether having a functional group including an unsaturated carbon bond in its skeleton is called a photosensitive polyphenylene ether. By the photosensitive polyphenylene ether, radical polymerizability due to active species such as radicals can be obtained.

Phenols satisfying condition 2 include 2-allyl-6-methylphenol, 2-allyl-6-ethylphenol, 2-allyl-6-phenylphenol, 2-allyl Base-6-styrylphenol, 2,6-divinylphenol, 2,6-diallylphenol, 2,6-diisopropenylphenol, 2,6-dibutenylphenol, 2, 6-diisobutenylphenol, 2,6-diisopentenylphenol, 2-methyl-6-styrylphenol, 2-vinyl-6-methylphenol, 2-vinyl-6-ethyl Phenol etc. may use only 1 type, and may use 2 or more types.

＜＜Phenols satisfying conditions 1 and 2＞＞ The phenols satisfying the condition 1 and the condition 2 have hydrogen atoms at the ortho-position and the para-position, and are phenols having a functional group including an unsaturated carbon bond. A polyphenylene ether obtained by using the phenol as a raw material phenol has a part of its structure branched by benzene rings bonded via ether at least at three positions of the ortho-position, the ortho-position, and the para-position, and has at least one unsaturated A carbon-bonded hydrocarbon group is used as a functional group.

Examples of phenols satisfying conditions 1 and 2 include o-vinylphenol, m-vinylphenol, o-allylphenol, m-allylphenol, 3-vinyl-6-methylphenol, 3-vinylphenol, Base-6-ethylphenol, 3-vinyl-5-methylphenol, 3-vinyl-5-ethylphenol, 3-allyl-6-methylphenol, 3-allyl-6- Ethylphenol, 3-allyl-5-methylphenol, 3-allyl-5-ethylphenol, etc. may use only 1 type, and may use 2 or more types.

<<Phenols that do not satisfy either of the conditions 1 and 2>> The raw material phenols used in the synthesis of the polyphenylene ether of the present invention may contain phenols that do not satisfy either of the conditions 1 and 2 from the viewpoint of adjusting the solubility and radical polymerizability due to the branched structure. .

Such raw material phenols include, for example, 2,6-dimethylphenol as phenols having a hydrogen atom at the para-position, no hydrogen atom at the ortho-position, and no functional group including an unsaturated carbon bond. , 2,3,6-trimethylphenol, 2-methyl-6-ethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-n-butylphenol, 2-methyl Base-6-phenylphenol, 2,6-diphenylphenol, 2,6-xylylphenol, etc., by forming ether bonds at the normal and para-positions of the benzene ring and polymerizing them linearly, Therefore, the branching structure is reduced and the solubility is reduced. Moreover, since it does not have a functional group containing an unsaturated carbon bond, radical polymerizability falls.

Moreover, as phenols which do not satisfy any one of the condition 1 and the condition 2, the phenol which does not have a hydrogen atom in a para position and an ortho position, and does not have a functional group containing an unsaturated carbon bond is also mentioned. The phenols can inhibit the polymerization reaction of polyphenylene ether. Such phenols that do not satisfy either of Condition 1 and Condition 2 may be used alone or in combination of two or more.

＜＜＜Polyphenylene ether A＞＞＞ The polyphenylene ether A in the present invention is obtained from raw material phenols including at least phenols satisfying condition 1 and phenols satisfying condition 2, and is the content of phenols satisfying condition 2 relative to the entire raw material phenols at the time of synthesis Polyphenylene ether having a weight average molecular weight of more than 40,000 and less than 200,000 is less than 20 mol%.

Polyphenylene ether A is a polyphenylene ether having a branched structure and functional groups containing unsaturated carbon bonds, and the ratio of the content of phenols satisfying condition 2 to the entire raw material phenols at the time of synthesis is lower than that of polyphenylene ether B , so the deterioration of dielectric properties caused by functional groups containing unsaturated carbon bonds is suppressed, and the polymerization reaction during synthesis is easy to proceed, and the weight average molecular weight is relatively large, thereby excellent development resistance.

Polyphenylene ether A has a weight average molecular weight of preferably more than 40,000 and 200,000 or less, more preferably 60,000 or more and 200,000 or less from the viewpoint of the balance between the developability of the unexposed part and the development resistance of the exposed part, and the number average molecular weight It is preferably from 10,000 to 30,000, more preferably from 15,000 to 20,000.

The content of phenols used in the synthesis of polyphenylene ether A that satisfies at least condition 1 may be 1 mol% or more and 99 mol% or less, preferably 5 mol% or more and 30 mol% or less, relative to the total raw material phenols during synthesis. Preferably, it is 5 mol% or more and 15 mol% or less, More preferably, it is 10 mol%.

The content of phenols used in the synthesis of polyphenylene ether A that satisfies at least condition 2 may be less than 20 mol%, preferably 1 mol% or more and less than 20 mol%, relative to the total phenols used as raw materials for synthesis. Preferably, it is 5 mol% or more and 15 mol% or less, More preferably, it is 10 mol%.

In the synthesis of polyphenylene ether A, phenols that do not satisfy either of Condition 1 or Condition 2 can be used within the range that does not impair the effect of the present invention.

＜＜＜Polyphenylene ether B＞＞＞ The polyphenylene ether B in the present invention is obtained from raw material phenols containing phenols satisfying at least condition 1 and phenols satisfying condition 2, and the ratio of the phenols satisfying condition 2 to the raw material at the time of synthesis is Polyphenylene ether with an overall phenol content of 20 mol % or more.

Polyphenylene ether B is a polyphenylene ether having a branched structure and functional groups containing unsaturated carbon bonds, and the content ratio of phenols satisfying condition 2 relative to the total phenols used in synthesis is higher than that of polyphenylene ether A , has more functional groups containing unsaturated carbon bonds, so it has excellent free radical polymerizability. On the other hand, since the phenols satisfying the condition 2 are difficult to undergo polymerization reaction and have a relatively small weight average molecular weight, they exhibit excellent developability.

The weight-average molecular weight of polyphenylene ether B is preferably from 5,000 to 40,000, and more preferably from 10,000 to 20,000 because radical polymerizability and developability are further improved. In addition, the number average molecular weight is preferably from 5,000 to 20,000, more preferably from 5,000 to 12,000.

The content of phenols used in the synthesis of polyphenylene ether B that satisfies at least condition 1 may be 1 mol% to 90 mol%, preferably 2 mol% to 50 mol%, with respect to the total raw material phenols at the time of synthesis. Preferably, it is not less than 5 mol% and not more than 20 mol%.

The content of phenols used in the synthesis of polyphenylene ether B that satisfies at least condition 2 may be 20 mol% or more, preferably 20 mol% or more and 90 mol% or less, more preferably 50 mol% with respect to the total phenols used as raw materials for synthesis. % above 90mol% below.

In the synthesis of polyphenylene ether B, phenols that do not satisfy either of Condition 1 or Condition 2 can be used within the range that does not impair the effect of the present invention.

＜<<Polyphenylene ether content>>> The content of polyphenylene ether (polyphenylene ether A and polyphenylene ether B) in the curable composition of the present invention is preferably 50~ 90% by mass, more preferably 60-80% by mass. In addition, the content ratio of polyphenylene ether A to polyphenylene ether B in the curable composition (polyphenylene ether A:polyphenylene ether B) is preferably 10:90~90:10 in terms of mass ratio, more preferably 25:75~75:25, in the case of improving the development resistance of the exposed part, it can be set to 50:50~75:25, in order to improve the photoradical polymerization (photosensitivity) and the developability of the unexposed part Under normal circumstances, it can be set to 25:75~50:50.

＜<<Manufacturing method of polyphenylene ether A and B>>> The polyphenylene ether A and polyphenylene ether B of the present invention can be produced by a conventional polyphenylene ether synthesis method except that the raw material phenols used are changed. For example, it can be produced by the synthesis method disclosed in International Publication No. 2020/017570.

Although the molecular weight of polyphenylene ether depends on the type of raw material phenols used, it can also be adjusted by changing the reaction temperature and reaction time when synthesizing polyphenylene ether.

＜<<<Compounds with functional groups that can undergo radical polymerization with unsaturated carbon bonds>>>> The compound having a functional group capable of radically polymerizing with an unsaturated carbon bond contained in the curable composition of the present invention (hereinafter also referred to as a radically polymerizable compound) has two or more structures that can be combined with the above-mentioned polyphenylene ether. Compounds with functional groups whose unsaturated carbon bonds undergo free radical polymerization. As the functional group that may undergo radical polymerization, known and commonly used functional groups can be used, for example, thiol group, allyl group and the like are exemplified.

Radical polymerizable compounds, for example, as compounds having a thiol group, trimethylolpropane ginseng (3-mercaptopropionate), ginseng-[(3-mercaptopropionyloxy)-ethyl]-iso Cyanurate, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), etc. Examples of compounds having an allyl group include triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, 1,4-cyclohexanedicarboxylic acid di- Allyl ester etc.

＜<<Content of compounds having functional groups that can undergo radical polymerization with unsaturated carbon bonds>>> The content of the radical polymerizable compound in the curable composition is preferably 1 to 99% by mass, more preferably 10 to 20% by mass relative to the polyphenylene ether in the curable composition.

＜＜＜＜Photofree Radical Generator＞＞＞＞ The photoradical generator contained in the curable composition of the present invention is a compound that generates free radicals by light irradiation (exposure), and causes the above-mentioned polyphenylene ether and radical polymerization compound to undergo free radicals by the generated free radicals. Polymerizes the exposed part and imparts development resistance to the exposed part.

As the photoradical generator, a conventional photoradical generator can be used. For example, benzoin ether series, acetophenone series, α-ketol series, aromatic sulfonyl chloride series, photoactive oxime series, benzoin series, diphenyl ketone series, diphenyl ketone series, ketal series, etc. series, thioxanthone series, acyl phosphine oxide series, etc.

Examples of benzoin ether-based photoradical generators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy -1,2-diphenylethan-1-one, anise, etc.

As an acetophenone-based photoradical generator, for example, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1 -[4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-2-methyl-1-phenyl-propane- 1-ketone, methoxyacetophenone, etc.

Examples of α-ketol-based photoradical generators include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2 -Methylpropan-1-one and the like.

As an aromatic sulfonyl chloride type photoradical generator, 2-naphthalenesulfonyl chloride etc. are mentioned, for example. As a photoactive oxime type photoinitiator, 1-phenyl-1, 2-propanedione-2-(O-ethoxycarbonyl)-oxime etc. are mentioned, for example.

Examples of the benzoin-based photoradical generating agent include benzoin and the like.

As the benzphenone-based photoradical generator, for example, benzphenone and the like are exemplified.

As the benzophenone photoradical generator, for example, benzophenone, benzoylbenzoic acid, 3,3´-dimethyl-4-methoxydiphenyl ketone, polyethylene diphenyl Phenyl ketone, α-hydroxycyclohexyl phenyl ketone, etc.

As a ketal type photoradical generator, benzyl dimethyl ketal etc. are mentioned, for example.

Examples of thioxanthone-based photoradical generators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, and Xanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone wait.

As an acylphosphine oxide-based photoradical generator, for example, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl) base)(2,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)n-butylphosphine oxide, bis(2,6-dimethoxybenzene Formyl)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylpropan-1-yl)phosphine oxide, bis (2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethyl Oxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzoyl) (1-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,6-bis Ethoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide , bis(2,4-dimethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4 -dipentyloxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-benzene propylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide , Bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide , 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethyl Benzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4 ,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, Bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)- 2,4-Di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2 ,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethoxybenzoyl-2, 4,6-Trimethylbenzoyl n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzene Formyl)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, tris(2- methylbenzoyl) phosphine oxide, etc.

These photoradical generators may use only 1 type, and may use 2 or more types.

＜<<Content of Photo Radical Generator>>> The content of the photoradical generator in the curable composition is preferably 0.1 to 10% by mass, more preferably 1 to 5% by mass, relative to the polyphenylene ether in the curable composition.

＜＜＜＜Solvent＞＞＞＞ The curable composition of the present invention may optionally contain a solvent in conjunction with steps such as blending and coating. As a solvent, it is preferable to be a solvent that can dissolve the above-mentioned polyphenylene ether. For example, in addition to solvents that may be used in the past such as chloroform, methylene chloride, toluene, etc., N-methyl-2-pyrrolidone (NMP ), tetrahydrofuran (THF), cyclohexanone, propylene glycol monomethyl ether acetate (PMA), diethylene glycol monoethyl ether acetate (CA), methyl ethyl ketone, ethyl acetate, etc. These may use only 1 type, and may use 2 or more types.

＜＜＜＜Other Ingredients＞＞＞＞ The curable composition of the present invention may contain other components in addition to the above-mentioned components within the range that does not impair the effect of the present invention. For example, inorganic fillers such as silicon dioxide, peroxides such as α,α'-bis(t-butylperoxym-isopropyl)benzene, polyphenylene ethers other than the above-mentioned polyphenylene ethers, maleic acid, etc. Resins and polymer components such as imide resins and styrene-based elastomers, sensitizers, adhesive additives, surfactants, leveling agents, plasticizers, adhesives, colorants, fibers, silane coupling agents, Flame retardant, cellulose nanofiber, dispersant, thermosetting catalyst, thickener, defoamer, antioxidant, rust inhibitor, adhesion imparting agent, etc. These components can be blended in appropriate amounts depending on the application and the like. As an example, when improving the dielectric properties, the content of the peroxide in the curable composition is preferably 0.1 to 10% by mass, more preferably 1% by mass, relative to the polyphenylene ether in the curable composition. ~5% by mass. These components may be used individually by 1 type, respectively, and may use it in combination of 2 or more types.

＜＜＜＜Dry Film＞＞＞＞＞ The dry film has a resin layer made of the curable composition of the present invention on the film material. The dry film is used by laminating a resin layer in contact with a substrate.

The dry film is uniformly coated with a curable composition on the carrier film (support film) by an appropriate method such as a knife coater, a lip die coater, a chip coater, a film coater, etc., and make it It is dried to form the aforementioned resin layer, preferably manufactured by laminating a cover film (protective film) thereon. The cover film and the carrier film can use the same film material or different films.

The film material of the carrier film and the cover film can be any conventional one used for dry film.

As the carrier film, thermoplastic films such as polyester films such as polyethylene terephthalate having a thickness of 2 to 150 μm can be used, for example.

A polyethylene film, a polypropylene film, etc. can be used as a cover film, but it is preferable that the adhesive force with a resin layer is smaller than a carrier film.

The film thickness of the resin layer on the dry film is preferably less than 100 μm, more preferably in the range of 5-50 μm.

＜＜＜＜hardened product＞＞＞＞＞ The cured product can be produced using a curable composition or a dry film having a resin layer made of the curable composition.

The curable composition of this embodiment is generally suitable for negative photolithography. Hereinafter, a method of manufacturing a patterned film that is a cured product of the curable composition of the present embodiment will be described by applying the curable composition of the present embodiment to negative photolithography.

First, as step 1, a curable composition is applied on a substrate and dried to form a resin layer, or a dry film is laminated on a substrate to transfer a resin layer composed of a curable composition. As a method of coating the curable composition on the base material, a method conventionally used for coating a curable composition can be used, for example, using a spin coater, a rod coater, a knife coater, a curtain coater, etc. A method of coating with a curtain coater, a screen printer, or the like, a method of spray coating with a spray coater, and an inkjet method, etc. can also be used.

As a drying method of the coating film, methods such as air drying, heat drying with an oven or a hot plate, and vacuum drying can be used. Moreover, the drying conditions of a coating film are not specifically limited, Natural drying, ventilation drying, or heat drying can be performed at 60-130 degreeC for 1-30 minutes.

The substrate is not particularly limited, and substrates made of semiconductor substrates such as silicon wafers, wiring boards, various resins, metals, and the like can be widely used.

Next, as step 2, the resin layer formed on the base material is irradiated with light (exposure) through a photomask having a pattern or directly in a pattern form. In addition, in the method of laminating a dry film, the film material is peeled off and exposed, or when the film material is light-transmitting, the film material is exposed with the film material remaining on the resin layer, and then the film material is peeled off. For exposure, light of a wavelength capable of activating the photoradical polymerization initiator is used. Specifically, it is preferable that the maximum wavelength is within the range of 350 to 410 nm. As the exposure apparatus, a contact aligner, a mirror projector, a stepper, a laser direct exposure apparatus, etc. can be used.

Next, as Step 3, the resin layer is treated with a developing solution. Thereby, the unexposed part of the resin layer can be removed to form a pattern film. After developing, the resin layer may be washed with a rinse solution if necessary.

As the method used for development, any method can be selected from conventionally known photoresist developing methods, such as a rotary spray method, a paddle method, a dipping method with ultrasonic treatment, and the like.

As the developer, a solvent that dissolves polyphenylene ether as a main component of the curable composition can be used, and an organic solvent is preferably used in order to prevent corrosion of circuits and the like. For example, in addition to solvents such as chloroform, methylene chloride, and toluene, N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), cyclohexanone, and propylene glycol monomethyl ether acetate (PMA) can be used Solvents such as , diethylene glycol monoethyl ether acetate (CA), methyl ethyl ketone, and ethyl acetate may be used alone or in combination of two or more. In addition, in the developing solution, from the viewpoint of adjusting the development speed, solvents other than the above-mentioned organic solvents may be combined, and an appropriate amount of a surfactant or the like may be contained as necessary.

As the rinsing liquid, distilled water, methanol, ethanol, isopropanol and the like are exemplified.

In addition, as step 5, the patterned film may be heated if necessary. The heating temperature is not particularly limited, for example, heating at 100 to 220° C. for about 30 to 120 minutes or the like. As the atmosphere (gas) at this time, air may be used, and inert gases such as nitrogen and argon may be used.

＜<<<<Electronic Parts>>>>> The electronic component has the hardened product of the above-mentioned embodiment. Since the cured product of the present embodiment has excellent dielectric properties and heat resistance, it can be used in various applications as a material constituting the electronic component.

Its use is not particularly limited, but preferred examples include high-capacity high-speed communications represented by the fifth generation communication system (5G), and insulation materials in electronic components such as millimeter-wave radars for automotive ADAS (advanced driver assistance systems) . [Example]

＜＜＜Synthesis of Polyphenylene Ether A＞＞＞ ＜＜Synthesis of PPEA-1＞＞ In a 3L two-necked eggplant-shaped flask, add di-μ-hydroxy-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)]chloride (Cu/TMEDA) 2.6 g, and 3.18 mL of tetramethylethylenediamine (TMEDA) were fully dissolved, and oxygen was supplied at a rate of 100 ml/min. A raw material solution was prepared by dissolving 89.1 g (90 mol %) of 2,6-dimethylphenol as raw material phenols and 10.9 g (10 mol %) of 2-allylphenol in 1.5 L of toluene. This raw material solution was dripped into the flask, and it was made to react at 40 degreeC for 10 hours, stirring at the rotation speed of 600 rpm. After the reaction, reprecipitate with a mixture of 20 L of methanol: 22 mL of concentrated hydrochloric acid, take it out by filtration, and dry it at 80° C. for 24 hours to obtain PPEA-1. The number average molecular weight of PPEA-1 was 17,500, and the weight average molecular weight was 192,000.

＜＜Synthesis of PPEA-2＞＞ In the above synthesis method of PPEA-1, PPEA-2 was obtained by the same method except that the reaction time was set to 8 hours. The number average molecular weight of PPEA-2 was 19,000, and the weight average molecular weight was 84,600.

＜＜Synthesis of PPEA-3＞＞ In the above synthesis method of PPEA-1, except that the reaction time was set to 6 hours, PPEA-3 was obtained by the same method. The number average molecular weight of PPEA-3 was 14,500, and the weight average molecular weight was 50,000.

＜＜Synthesis of PPEA-4＞＞ In the above synthesis method of PPEA-1, PPEA-4 was obtained by the same method except that the reaction time was set to 5 hours. The number average molecular weight of PPEA-4 was 12,000, and the weight average molecular weight was 36,000.

＜<<Synthesis of polyphenylene ether B>>> ＜＜Synthesis of PPEB-1＞＞ In a 3L two-necked eggplant-shaped flask, add di-μ-hydroxy-bis[(N,N,N',N'-tetramethylethylenediamine)copper(II)]chloride (Cu/TMEDA) 0.050 g and 0.0047 g of tetramethylethylenediamine (TMEDA) were fully dissolved, and oxygen was supplied at a rate of 50 ml/min. 8.8g (80mol%) of 2,6-dimethylphenol as raw material phenols and 0.67g (10mol%) of 2-allyl-6-methylphenol and 1.2g (10mol%) of 2-allylphenol It was dissolved in 60 mL of toluene to prepare a raw material solution. This raw material solution was dripped into the flask, and it was made to react at 40 degreeC for 18 hours, stirring at the rotation speed of 600 rpm. After the reaction, reprecipitate with a mixture of methanol 1.2L:concentrated hydrochloric acid 4mL, filter it out, and dry it at 80°C for 24 hours to obtain PPEB-1. The number average molecular weight of PPEB-1 was 5,600, and the weight average molecular weight was 11,500.

＜＜Synthesis of PPEB-2＞＞ In the synthesis method of the above-mentioned PPEB-1, in addition to changing 2,6-dimethylphenol as raw material phenols to 5.5g (50mol%) and changing 2-allyl-6-methylphenol to 5.3g ( 40mol%), the same method was used to obtain PPEB-2. The number average molecular weight of PPEB-2 was 5,400, and the weight average molecular weight was 11,200.

＜＜Synthesis of PPEB-3＞＞ In the synthesis method of PPEB-1 mentioned above, in addition to changing 2,6-dimethylphenol as raw material phenols to 1.1g (10mol%) and changing 2-allyl-6-methylphenol to 10.7g ( 80mol%), the same method was used to obtain PPEB-3. The number average molecular weight of PPEB-2 was 5,600, and the weight average molecular weight was 14,000.

＜＜＜Preparation of curable composition＞＞＞ <<Example 1>> PPEA-1: 75 parts by mass, PPEB-3: 25 parts by mass, and phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (manufactured by IGM Resins Co. : trade name "Omnirad 819"): 3 parts by mass, and trimethylolpropane ginseng (3-mercaptopropionate) as a thiol group-containing compound (manufactured by SC Organic Chemicals Co., Ltd.: trade name "TMMP") : 20 parts by mass, add cyclohexanone: 400 parts by mass, mix and stir at 40°C for 30 minutes to completely dissolve. Next, α,α'-bis(t-butylperoxym-isopropyl)benzene (manufactured by NOF Co., Ltd.: trade name "PERBUTYL P") as a peroxide: 2 parts by mass was blended with Stir with an electromagnetic stirrer to obtain the coating of the tree hardening composition of Example 1.

＜<Example 2~10, Comparative Example 1~6>> Except that each component and content were the components and values shown in Table 1, curable compositions were prepared in the same manner as in Example 1, and coating materials of curable compositions in Examples 2-13 and Comparative Examples 1-3 were obtained.

＜＜＜Evaluation＞＞＞ The following evaluations were performed on each curable composition and the cured film obtained by curing each curable composition. Table 1 shows the evaluation results.

<<Photosensitivity and Developability Evaluation>> The paint of each curable composition was applied on a silicon wafer using a spin coater so that the film thickness after drying was about 3 μm, and the coating was heated at 80 Dry at ℃ for 1 minute to form a resin layer composed of each curable composition. Afterwards, the silicon wafer formed with the resin layer was cut into a shape of 2.5×15 cm, which was used as a test sample for photosensitivity and developability. The resin layer of each test sample was irradiated with light with a wavelength of 365nm of 0 (unexposed), 400, 800, 1200, 1600, and 2000 mJ/ ^cm2 in terms of cumulative light intensity, and then dipped in cyclohexanone for 10 seconds for development. After drying the test sample after development, the thickness of the remaining resin layer at each exposure amount was measured with a stylus surface shape measuring device. Based on the difference between the remaining film thickness of the unexposed part and the remaining film thickness of each exposed part (developing contrast), the possibility of photolithography was evaluated by the following criteria. (Evaluation Criteria) ◎◎: Sufficient development contrast was obtained at an exposure of 800 mJ/cm ² or more. ◎: Sufficient development contrast was obtained with an exposure of 1200 mJ/cm ² or more. ◯: Sufficient development contrast was obtained at an exposure of 2000 mJ/cm ² . Δ: Slight development contrast was obtained with an exposure of 2000 mJ/cm ² . x: The exposure part did not acquire development resistance, or the non-exposed part was not developed, and the image development contrast was not obtained.

＜＜Dielectric properties＞＞ Each curable composition was applied to the glossy surface of copper foil with a thickness of 18 μm by an applicator so that the film thickness after drying would be 30 μm, and dried at 90° C. for 30 minutes in a hot-air circulation drying oven. Next, after curing in a non-oxidizing oven at 200° C. for 1 hour, a cured product (cured film) composed of each composition was obtained by etching the copper foil.

The produced cured film was cut into length 80mm, width 45mm and used as a test piece, and relative permittivity Dk and dielectric tangent Df were measured by SPDR (Split Post Dielectric Resonator) resonator method. As a measuring device, a vector network analyzer E5071C manufactured by Keysight Technologies Co., Ltd., an SPDR resonator, and a calculation program manufactured by QWED Corporation were used. The conditions were set to a frequency of 10 GHz and a measurement temperature of 25°C.

Claims (7)

A photosensitive composition comprising: polyphenylene ether A, polyphenylene ether B, a compound having a functional group capable of free-radical polymerization with an unsaturated carbon bond, and a photoradical generator, The polyphenylene ether A and the polyphenylene ether B are obtained from raw material phenols including phenols satisfying at least the following condition 1 and phenols satisfying at least the following condition 2, respectively, The polyphenylene ether A-based weight average molecular weight is more than 40,000 and not more than 200,000, and the content of phenols satisfying condition 2 is less than 20 mol% with respect to the entire raw material phenols at the time of synthesis, The polyphenylene ether B-based content of phenols satisfying condition 2 is 20 mol% or more relative to the entire raw material phenols at the time of synthesis, (Condition 1) have hydrogen atoms in the ortho and para positions; (Condition 2) It has a hydrogen atom at the para position, and has a functional group including an unsaturated carbon bond. The photosensitive composition according to claim 1, wherein the polyphenylene ether B has a weight average molecular weight of 5,000 to 40,000. The photosensitive composition according to claim 1 or 2, wherein the content ratio of the aforementioned polyphenylene ether A to the aforementioned polyphenylene ether B (polyphenylene ether A:polyphenylene ether B) is 25:75~ in terms of mass ratio 75:25. The photosensitive composition according to any one of Claims 1 to 3, wherein the above-mentioned functional groups capable of free-radical polymerization with unsaturated carbon bonds are thiol groups and/or allyl groups. A dry film having a resin layer made of the photosensitive composition according to any one of claims 1-4. A cured product, which is a cured product of the photosensitive composition according to any one of claims 1 to 4 or the resin layer according to claim 5. An electronic component having the hardened product according to claim 6.