TW202342587A - polyether resin - Google Patents

Abstract

The present invention addresses the problem of providing a polyether resin having exceptional dielectric characteristics. The solution to the problem addressed by the present invention is a polyether resin having a repeating unit represented by formula (1). Each symbol is as in the accompanying description.

Description

polyether resin

The present invention relates to polyether resins.

Printed wiring boards, which are widely used in various electronic devices, are required to be thinner or have fine wiring of circuits for the purpose of miniaturization and high functionality of electronic devices.

As a manufacturing technology of printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductive layers are alternately stacked is known. In the build-up manufacturing method, generally, the insulating layer is formed by thermally hardening or photohardening the resin composition. As such a resin composition, for example, the resin composition disclosed in Patent Document 1 is known. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2019-66792

[Problem to be solved by the invention]

In recent years, as communication in communication equipment has become faster and larger, resins used in the manufacture of semiconductor packaging substrates for communication equipment are required to have lower dielectric tangents, that is, better dielectric properties. In addition, in order to ensure further precision, resin compositions used in the production of semiconductor packaging substrates are required to have better resolution.

The present invention was made in view of the above-mentioned problems, and its object is to provide a resin with excellent dielectric properties. Furthermore, the object is to provide a resin composition with better resolution. [Means used to solve problems]

As a result of intensive research, the present inventors newly discovered a polyether resin having excellent dielectric properties, and completed the present invention. Furthermore, it was also discovered that a resin composition using such a polyether resin has better resolution.

That is, the present invention includes the following contents. [1] A polyether resin having formula (1):

[In the formula, R ¹ and R ² independently represent a hydrogen atom, -CN, -NO ₂ , -COH, -R, -OR, -COR, -COOR, -CONHR, -CONR ₂ , -SR, -SOR , or -SO ₂ R, R ¹ and R ² can also be bonded together to form a non-aromatic ring that may have a substituent; R each independently represents an alkyl group that may have a substituent, or an alkenyl group that may have a substituent, or an aryl group that may have a substituent; R ³ and R ⁴ each independently represent a substituent; Ring X ¹ and Ring X ² each independently represent an aromatic carbocyclic ring that may have a substituent; Y represents a single bond or an organic group; a represents 0 or 1; p and q are repeating units that independently represent 0, 1, 2, 3 or 4]. [2] The polyether resin of [1] above, which has formula (3):

[In the formula, R ¹ and R ² independently represent a hydrogen atom, -R, -COR, or -COOR. R ¹ and R ² can also be bonded together to form a non-aromatic ring that may have a substituent; R is Each independently represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a substituent; R ^A and R ^B independently represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent. R ^A and R ^B may also be bonded together to form a non-aromatic ring that may have a substituent; a and b represent 0 or 1 independently; p, q, r and s represent repeating units representing 0, 1, 2, 3 or 4 respectively. [3] The polyether resin of [2] above, when a is 0, s is 1 or more, and at least one of R ⁶ is an alkyl group with a carbon number of 4 or more; when a is 1 and b is 0, r The total of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is an alkyl group with more than 4 carbon atoms; when a is 1 and b is 1, (1) the total of r and s is 1 or more, and R At least one of ⁵ and R ⁶ is an alkyl group with 4 or more carbon atoms, and/or (2-1) R ^A and ^RB represent a hydrogen atom or an alkyl group, and at least one of them is an alkyl group with 4 or more carbon atoms, Or (2-2) R ^A and R ^B are bonded together to form a non-aromatic saturated carbocyclic ring with a monocyclic ring system of more than 5 members that can be substituted by an alkyl group, or a bicyclic ring with more than 6 members that can be substituted by an alkyl group. Non-aromatic saturated carbocyclic rings above the ring system. [4] The polyether resin according to any one of the above [1] to [3] has a weight average molecular weight of 5,000 or more. [5] The polyether resin according to any one of the above [1] to [4], wherein the dielectric tangent (Df) is 0.012 or less when measured at 5.8 GHz and 23°C. [6] An insulating material containing the polyether resin according to any one of the above [1] to [5]. [7] A resin composition containing the polyether resin according to any one of the above [1] to [5], and a curing cross-linking agent. [8] A resin composition containing the polyether resin according to any one of the above [1] to [5], a photocurable cross-linking agent, and a photopolymerization initiator. [9] The resin composition of [8] above, which further contains a photosensitizer. [10] A resin sheet having a support body and a resin composition layer formed of the resin composition according to any one of the above [7] to [9] provided on the support body. [11] A semiconductor packaging substrate including an insulating layer formed by a cured product of the resin composition according to any one of [7] to [9] above. [12] A semiconductor device including the semiconductor packaging substrate of [11] above. [13] A method of manufacturing a semiconductor packaging substrate, which includes the following steps (I) to (III) in sequence; (I) Forming on the circuit substrate a resin composition as described in [8] or [9] above The steps of forming the resin composition layer, (II) the step of irradiating the resin composition layer with active light, and (III) the step of developing the resin composition layer. [Effects of the invention]

According to the present invention, a polyether resin excellent in dielectric properties can be provided. In addition, a resin composition with better resolution can be provided.

Hereinafter, the present invention will be described in detail based on its suitable embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented within the scope without departing from the patentable scope of the present invention and its equivalent range.

＜Polyether resin＞ The polyether resin of the present invention has formula (1):

[In the formula, R ¹ and R ² independently represent a hydrogen atom, -CN, -NO ₂ , -COH, -R, -OR, -COR, -COOR, -CONHR, -CONR ₂ , -SR, -SOR , or -SO ₂ R, R ¹ and R ² can also be bonded together to form a non-aromatic ring that may have a substituent; R each independently represents an alkyl group that may have a substituent, or an alkenyl group that may have a substituent, or an aryl group that may have a substituent; R ³ and R ⁴ each independently represent a substituent; Ring X ¹ and Ring X ² each independently represent an aromatic carbocyclic ring that may have a substituent; Y represents a single bond or an organic group; a represents 0 or 1; p and q are repeating units that independently represent 0, 1, 2, 3 or 4]. Such polyether resin has better dielectric properties. Therefore, it can be suitably used as an insulating material in printed wiring boards and the like.

R ¹ and R ² independently represent a hydrogen atom, -CN, -NO ₂ , -COH, -R, -OR, -COR, -COOR, -CONHR, -CONR ₂ , -SR, -SOR, or -SO ₂ R, R ¹ and R ² may also be bonded together to form a non-aromatic ring which may have a substituent.

R ¹ and R ² , in one embodiment, are preferably independently hydrogen atoms, -CN, -NO ₂ , -COH, -R, -COR, -COOR, -CONHR, or -CONR ₂ , R ¹ and R ² may also be bonded together to form a non-aromatic ring which may have a substituent.

In one embodiment, R ¹ and R ² are preferably independently hydrogen atoms, -CN, -NO ₂ , -COH, -R, -COR, or -COOR. R ¹ and R ² can also be bonded together. , to form a non-aromatic ring that may have substituents.

In one embodiment, R ¹ and R ² are preferably independently hydrogen atoms, -R, -COR, or -COOR. R ¹ and R ² can also be bonded together to form a non-substituent-containing substituent. aromatic ring.

In one embodiment, R ¹ and R ² are preferably each independently a hydrogen atom, -COR, or -COOR. R ¹ and R ² may also be bonded together to form a non-aromatic ring that may have a substituent.

The "substituent" in the "non-aromatic ring which may have a substituent" formed by R ¹ and R ² is not particularly limited, and examples thereof include halogen atoms, -NO ₂ , -CN, -COH, -OH, and -SH. , -NH ₂ , -COOH, -R ^x , -COR ^x , -OR ^x , -SR ^x , -SOR ^x , -SO ₂ R ^x , -NHR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , -NHCOR ^x , =O, etc. are monovalent substituents or divalent substituents.

^R Alkenyloxy, aryloxy, aralkyloxy, alkylcarbonyl, alkenylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, arylcarbonyloxy, aralkyl Carbonyloxy, alkoxycarbonyl, alkenyloxycarbonyl, aryloxycarbonyl, aralkyloxycarbonyl, alkylamino, di(alkyl)amine, alkenylamine, alkylalkenylamine , alkylcarbonylamine group, alkenylcarbonylamino group, alkylaminemethyl group, and alkenylaminemethyl group substituted alkyl group; (2) can be selected from halogen atom, nitro group, cyano group, Hydroxy, amine, aryl, alkyl-substituted aryl, alkenyl-substituted aryl, alkoxy, alkenyloxy, aryloxy, aralkyloxy, alkylcarbonyl, alkenylcarbonyl, aromatic Alkylcarbonyl, aralkylcarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, arylcarbonyloxy, aralkylcarbonyloxy, alkoxycarbonyl, alkenyloxycarbonyl, aryloxycarbonyl, aralkyl Oxycarbonyl, alkylamino, di(alkyl)amine, alkenylamine, alkylalkenylamine, alkylcarbonylamino, alkenylcarbonylamino, alkylamineformylamine, and alkenyl An alkenyl group substituted with an amine carboxyl group; or (3) may be selected from the group consisting of a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and an alkyl group. Substituted aryl, alkenyl-substituted aryl, alkoxy, alkenyloxy, aryloxy, aralkyloxy, alkylcarbonyl, alkenylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylcarbonyl Oxygen, alkenylcarbonyloxy, arylcarbonyloxy, aralkylcarbonyloxy, alkoxycarbonyl, alkenyloxycarbonyl, aryloxycarbonyl, aralkyloxycarbonyl, alkylamino, di( Alkyl)amine, alkenylamine, alkylalkenylamine, alkylcarbonylamino, alkenylcarbonylamino, alkylaminemethyl, and alkenylaminemethyl substituted aryl groups .

A halogen atom refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

Alkyl means a linear, branched chain and/or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 10, and still more preferably 1 to 6. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, and neopentyl base, tert-pentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, tert-octyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, etc.

Alkenyl means a linear, branched chain and/or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. Unless otherwise specified, the number of carbon atoms in the alkenyl group is preferably 2 to 18, more preferably 2 to 10, and still more preferably 2 to 6. Examples of alkenyl groups include vinyl, propenyl (allyl, 1-propenyl, isopropenyl), butenyl (1-butenyl, crotyl, methallyl, isocrotyl, etc.) , Pentenyl (1-pentenyl, etc.), hexenyl (1-hexenyl, etc.), heptenyl (1-heptenyl, etc.), octenyl (1-octenyl, etc.), ring Pentenyl (2-cyclopentenyl, etc.), cyclohexenyl (3-cyclohexenyl, etc.), etc.

Aryl group means a monovalent aromatic hydrocarbon group obtained by removing one hydrogen atom of an aromatic carbon ring. Unless otherwise specified, the carbon number of the aryl group is preferably 6 to 18, and particularly preferably 6 to 10. Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, and the like.

Aralkyl group means an alkyl group substituted by one or more (preferably one) aryl groups. Unless otherwise specified, the number of carbon atoms in the aralkyl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of the aralkyl group include benzyl, phenethyl, hydrocinnamyl, α-methylbenzyl, α-cumyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like.

An aryl group substituted by an alkyl group means an aryl group substituted by one or more alkyl groups. Unless otherwise specified, the carbon number of the aryl group substituted by the alkyl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of aryl groups substituted by alkyl groups include 4-methylphenyl, 3-methylphenyl, 2-methylphenyl, 2,4-dimethylphenyl, and 3,5-dimethylphenyl. base, 2,4,6-trimethylphenyl, 4-ethylphenyl, 3-ethylphenyl, 2-ethylphenyl, etc.

An aryl group substituted by an alkenyl group means an aryl group substituted by one or more alkenyl groups. Unless otherwise specified, the carbon number of the alkenyl-substituted aryl group is preferably 8 to 20, and particularly preferably 8 to 12. Examples of alkenyl-substituted aryl groups include 4-vinylphenyl, 3-vinylphenyl, 2-vinylphenyl, 2,4-divinylphenyl, and 3,5-divinylphenyl. base, 4-isopropenylphenyl, 3-isopropenylphenyl, 2-isopropenylphenyl, 4-allylphenyl, etc.

The alkoxy group means a univalent group in which an alkyl group is bonded to an oxygen atom (that is, a group represented by R ^s1 -O- (R ^s1 is an alkyl group)). Unless otherwise specified, the number of carbon atoms in the alkoxy group is preferably 1 to 18, more preferably 1 to 10, and still more preferably 1 to 6. Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and the like.

The alkenyloxy group means a monovalent group in which an alkenyl group is bonded to an oxygen atom (that is, a group represented by R ^s2 -O- (R ^s2 is an alkenyl group)). Unless otherwise specified, the carbon number of the alkenyloxy group is preferably 2 to 18, more preferably 2 to 10, and still more preferably 2 to 6. Examples of the alkenyloxy group include vinyloxy group, propenyloxy group (allyloxy group, 1-propenyloxy group, isopropenyloxy group) and the like.

The aryloxy group means a monovalent group in which an aryl group is bonded to an oxygen atom (that is, a group represented by R ^s3 -O- (R ^s3 is an aryl group)). Unless otherwise specified, the carbon number of the aryloxy group is preferably 6 to 18, and particularly preferably 6 to 10. Examples of the aryloxy group include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, and the like.

The aralkoxy group means a monovalent group in which an aralkyl group is bonded to an oxygen atom (that is, a group represented by R ^s4 -O- (R ^s4 is an aralkyl group)). Unless otherwise specified, the number of carbon atoms in the aralkoxy group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of the aralkoxy group include benzyloxy group, α-methylbenzyloxy group, and the like.

Alkylcarbonyl group means a monovalent group in which an alkyl group is bonded to one side of a carbonyl group (that is, a group represented by R ^s1 -C(=O)-(R ^s1 is an alkyl group)). Unless otherwise specified, the carbon number of the alkylcarbonyl group is preferably 2 to 19, more preferably 2 to 11, and still more preferably 2 to 7. Examples of the alkylcarbonyl group include an acetyl group, a propyl group, a butyl group, and the like.

Alkenylcarbonyl group means a monovalent group in which an alkenyl group is bonded to one of the carbonyl groups (that is, a group represented by R ^s2 -C(=O)-(R ^s2 is an alkenyl group)). Unless otherwise specified, the carbon number of the alkenyl carbonyl group is preferably 3 to 19, more preferably 3 to 11, and still more preferably 3 to 7. Examples of the alkenylcarbonyl group include vinylcarbonyl, propenylcarbonyl (allylcarbonyl, 1-propenylcarbonyl, isopropenylcarbonyl) and the like.

Arylcarbonyl means a monovalent group in which an aryl group is bonded to one of the carbonyl groups (that is, a group represented by R ^s3 -C(=O)-(R ^s3 is an aryl group)). Unless otherwise specified, the carbon number of the arylcarbonyl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of the arylcarbonyl group include benzyl group, 1-naphthylyl group, 2-naphthylyl group, and the like.

The aralkylcarbonyl group means a monovalent group in which an aralkyl group is bonded to one of the carbonyl groups (that is, a group represented by R ^s4 -C(=O)-(R ^s4 is an aralkyl group)). Unless otherwise specified, the carbon number of the aralkylcarbonyl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of the aralkylcarbonyl group include benzylcarbonyl, α-methylbenzylcarbonyl, and the like.

The alkylcarbonyloxy group means a monovalent group in which an alkylcarbonyl group is bonded to an oxygen atom (that is, a group represented by R ^s1 -C(=O)-O-(R ^s1 is an alkyl group)). Unless otherwise specified, the carbon number of the alkylcarbonyloxy group is preferably 2 to 19, more preferably 2 to 11, and still more preferably 2 to 7. Examples of the alkylcarbonyloxy group include an acetyloxy group, a propyloxy group, a butyloxy group, and the like.

Alkenylcarbonyloxy group means a monovalent group in which an alkenylcarbonyl group is bonded to an oxygen atom (that is, a group represented by R ^s2 -C(=O)-O-(R ^s2 is an alkenyl group)). Unless otherwise specified, the carbon number of the alkenylcarbonyloxy group is preferably 3 to 19, more preferably 3 to 11, and still more preferably 3 to 7. Examples of the alkenylcarbonyloxy group include vinylcarbonyloxy, propenylcarbonyloxy (allylcarbonyloxy, 1-propenylcarbonyloxy, isopropenylcarbonyloxy) and the like.

The arylcarbonyloxy group means a monovalent group in which an arylcarbonyl group is bonded to an oxygen atom (that is, a group represented by R ^s3 -C(=O)-O-(R ^s3 is an aryl group)). Unless otherwise specified, the carbon number of the arylcarbonyloxy group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of the arylcarbonyloxy group include benzyloxy, 1-naphthyloxy, and 2-naphthyloxy.

The aralkylcarbonyloxy group means a monovalent group in which an aralkylcarbonyl group is bonded to an oxygen atom (that is, a group represented by R ^s4 -C(=O)-O-(R ^s4 is an aralkyl group)). Unless otherwise specified, the carbon number of the aralkylcarbonyl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of the aralkylcarbonyloxy group include benzylcarbonyloxy group, α-methylbenzylcarbonyloxy group, and the like.

The alkoxycarbonyl group means a monovalent group in which an alkoxy group is bonded to one of the carbonyl groups (that is, a group represented by R ^s1 -OC(=O)-(R ^s1 is an alkyl group)). Unless otherwise specified, the carbon number of the alkoxycarbonyl group is preferably 2 to 19, more preferably 2 to 11, and still more preferably 2 to 7. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, and the like.

Alkenyloxycarbonyl group means a monovalent group in which an alkenyloxy group is bonded to one of the carbonyl groups (that is, a group represented by R ^s2 -OC(=O)-(R ^s2 is an alkenyl group)). Unless otherwise specified, the carbon number of the alkenyloxycarbonyl group is preferably 3 to 19, more preferably 3 to 11, and still more preferably 3 to 7. Examples of the alkenyloxycarbonyl group include vinyloxycarbonyl, propenyloxycarbonyl (allyloxycarbonyl, 1-propenyloxycarbonyl, isopropenyloxycarbonyl) and the like.

The aryloxycarbonyl group means a monovalent group in which an aryloxy group is bonded to one of the carbonyl groups (that is, a group represented by R ^s3 -OC(=O)-(R ^s3 is an aryl group)). Unless otherwise specified, the carbon number of the aryloxycarbonyl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of the aryloxycarbonyl group include phenoxycarbonyl, 1-naphthyloxycarbonyl, 2-naphthyloxycarbonyl, and the like.

The aralkoxycarbonyl group means a monovalent group in which an aralkoxy group is bonded to one of the carbonyl groups (that is, a group represented by R ^s4 -OC(=O)-(R ^s4 is an aralkyl group)). Unless otherwise specified, the carbon number of the aralkylcarbonyl group is preferably 7 to 19, and particularly preferably 7 to 11. Examples of the aralkoxycarbonyl group include benzyloxycarbonyl group, α-methylbenzyloxycarbonyl group, and the like.

Alkylamino group means an amino group monosubstituted by an alkyl group (that is, a group represented by R ^s1 -NH- (R ^s1 is an alkyl group)). Unless otherwise specified, the carbon number of the alkylamine group is preferably 1 to 18, more preferably 1 to 10, and still more preferably 1 to 6. Examples of the alkylamino group include N-methylamino group, N-ethylamino group, N-propylamino group, and the like. Di(alkyl)amine group means an amino group disubstituted with an alkyl group (that is, a group represented by (R ^s1 -) ₂ N- (R ^s1 is independently an alkyl group)). Unless otherwise specified, the carbon number of the di(alkyl)amine group is preferably 2 to 18, more preferably 2 to 10, and still more preferably 2 to 6. Examples of di(alkyl)amine groups include N,N-dimethylamino group, N,N-diethylamino group, N-ethyl-N-methylamino group, and N,N-dipropyl group. Amino group etc.

Alkenylamine group means an amine group monosubstituted by an alkenyl group (that is, a group represented by R ^s2 -NH- (R ^s2 is an alkenyl group)). Unless otherwise specified, the carbon number of the alkenylamine group is preferably 2 to 19, more preferably 2 to 11, and still more preferably 2 to 7. Examples of the alkenylamine group include N-vinylamine group, N-allylamino group, and the like. Alkyl alkenyl amino group means an amino group substituted by both alkyl and alkenyl (i.e. (R ^s1 -) (R ^s2 -) N- (R ^s1 is an alkyl group, R ^s2 is an alkenyl group). base). Unless otherwise specified, the number of carbon atoms in the alkylalkenylamine group is preferably 3 to 19, more preferably 3 to 11, and still more preferably 3 to 7. Examples of the alkylalkenylamine group include N-methyl-N-vinylamine group, N-allyl-N-methylamino group, and the like.

Alkylcarbonylamino group means an amine group monosubstituted by an alkylcarbonyl group (that is, a group represented by R ^s1 -C(=O)-NH-(R ^s1 is an alkyl group)). Unless otherwise specified, the carbon number of the alkylcarbonylamino group is preferably 2 to 19, more preferably 2 to 11, and still more preferably 2 to 7. Examples of the alkylcarbonylamino group include N-acetylamino group, N-propylamino group, N-butylamino group, and the like.

Alkenylcarbonylamino group means an amine group monosubstituted by alkenylcarbonyl group (that is, a group represented by R ^s2 -C(=O)-NH-(R ^s2 is alkenyl)). Unless otherwise specified, the carbon number of the alkenylcarbonylamino group is preferably 3 to 20, more preferably 2 to 11, and still more preferably 2 to 7. Examples of the alkenylcarbonylamino group include N-vinylcarbonylamino group, N-allylcarbonylamino group, N-(1-propenylcarbonyl)amine group, N-isopropenylcarbonylamino group, and the like.

Alkylamineformyl group means an aminoformyl group monosubstituted by an alkyl group (that is, a group represented by R ^s1 -NH-C(=O)-(R ^s1 is an alkyl group)). Unless otherwise specified, the number of carbon atoms in the alkylamine carboxyl group is preferably 2 to 19, more preferably 2 to 11, and still more preferably 2 to 7. Examples of the alkylamineformyl group include N-methylaminoformyl group, N-ethylamineformyl group, N-propylamineformyl group, and the like.

Alkenylamineformyl group means an aminoformyl group monosubstituted by an alkenyl group (that is, a group represented by R ^s2 -NH-C(=O)-(R ^s2 is an alkenyl group)). Unless otherwise specified, the carbon number of the alkenylamine carboxyl group is preferably 3 to 20, more preferably 3 to 12, and still more preferably 3 to 8. Examples of the alkenylaminemethyl group include N-vinylaminemethyl group, N-allylaminemethyl group, and the like.

Non-aromatic ring means a ring other than an aromatic ring in which the entire ring is aromatic. A non-aromatic ring can be a non-aromatic carbocyclic ring that only uses carbon atoms as ring constituent atoms, or a non-aromatic heterocyclic ring that in addition to carbon atoms also has heteroatoms such as oxygen atoms, nitrogen atoms, sulfur atoms, etc. as ring constituent atoms. . The non-aromatic ring may be a monocyclic non-aromatic ring or a polycyclic non-aromatic ring, and may also include a condensed ring in which an aromatic ring is condensed on one part to become partially aromatic. The non-aromatic ring may be a saturated ring consisting only of single bonds, or an unsaturated ring having double bonds in addition to single bonds. The non-aromatic ring is preferably a non-aromatic ring with 3 to 21 members, more preferably a non-aromatic ring with 4 to 18 members, and even more preferably a non-aromatic ring with 5 to 14 members.

Suitable specific examples of the "non-aromatic ring" among the "non-aromatic rings that may have substituents" formed by R ¹ and R ² include cyclobutane ring, cyclopentane ring, cyclohexane ring, and cycloheptane ring. Alkane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, 1,3- Monocyclic non-aromatic carbocyclic rings such as cyclohexadiene ring and 1,4-cyclohexadiene ring; 1,3-dioxane ring, 1,3-dioxolane ring and tetrahydrogen Pyran ring, tetrahydrofuran ring, 2,3-dihydro-2H-pyran ring, 4,5-dihydro-2H-pyran ring, 2H-pyran ring, 4H-pyran ring, 2,3-di Hydrofuran ring, 2,5-dihydrofuran ring, monocyclic non-aromatic heterocyclic rings, etc.

When R ¹ and R ² form a "non-aromatic ring that may have a substituent", the formula (A) is:

[In the formula, each symbol is as above] The partial structures shown are preferably formulas (AA1) to (AA10) in one embodiment:

[In the formula, A ¹ and A ² independently represent -CO- or -CR ^a R ^b -; B ¹ and B ² represent independently -O-, -NR ^c - or -CR ^a R ^b -; C ¹ represents -O- or -NR ^c -; R ^a and R ^b independently represent a hydrogen atom or a substituent, and the two R ^a bonded to adjacent carbon atoms can also be bonded together to form a substituted The non-aromatic ring of the base, or the aromatic ring that may have substituents, R ^a and R ^b bonded to the same carbon atom may also be bonded together to form a non-aromatic ring that may have substituents; R ^c represents each independently A structure represented by a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group]; more preferably, it is a structure represented by formula (AA1) or (AA3); particularly preferably Formula (Aa1)~(Aa5):

[In the formula, each symbol is as above] Representation structure.

A ¹ and A ² independently represent -CO- or -CR ^a R ^b -; in one embodiment, preferably -CR ^a R ^b -.

B ¹ and B ² independently represent -O-, -NR ^c - or -CR ^a R ^b -; in one embodiment, preferably -O- or -CR ^a R ^b -.

C ¹ represents -O- or -NR ^c -; in one embodiment, it is preferably -O-.

R ^a and R ^b each independently represent a hydrogen atom or a substituent. The two R ^a bonded to adjacent carbon atoms can also be bonded together to form a non-aromatic ring that may have a substituent, or may have a substituent. For an aromatic ring, R ^a and R ^b bonded to the same carbon atom can also be bonded together to form a non-aromatic ring that may have substituents.

Suitable specific examples of the "non-aromatic ring" in the "non-aromatic ring which may have a substituent" formed by R ^a and R ^b or two R ^a include, for example, a cyclobutane ring, a cyclopentane ring, and a cyclopentane ring. Non-aromatic saturated carbocyclic rings of monocyclic systems such as hexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, etc.; bicyclic rings [ 2.2.1] Heptane ring (norbornane ring), bicyclo[4.4.0]decane ring (decalin ring), bicyclo[5.3.0]decane ring, bicyclo[4.3.0]nonane ring ( Octahydroindene ring), bicyclo[3.2.1]octane ring, bicyclo[5.4.0]undecane ring, bicyclo[3.3.0]octane ring, bicyclo[3.3.1]nonane ring, tricyclo[ 5.2.1.0 ^2,6 ] Decane ring (tetrahydrodicyclopentadiene ring), tricyclo [3.3.1.1 ^3,7 ] Decane ring (adamantane ring), tricyclo [6.2.1.0 ^2,7 ] Non-aromatic saturated carbocyclic rings with two or more ring systems such as undecane ring; indene ring, indene ring, tetrahydronaphthalene ring, 1,2-dihydronaphthalene ring, 1,4-dihydronaphthalene ring, fluorine ring , 9,10-dihydroanthracene ring, 9,10-dihydrophenanthrene ring, etc. are partially condensed with non-aromatic carbon rings containing aromatic rings (benzene rings, naphthalene rings, etc.).

The "substituent" represented by R ^a and R ^b and the "substituent" in the "aromatic ring which may have a substituent" formed by two R ^a are not particularly limited, and examples thereof include halogen atoms, -NO ₂ , - CN, -COH, -OH, -SH, -NH ₂ , -COOH, -R ^x , -COR ^x , -OR ^x , -SR ^x , -SOR ^x , -SO ₂ R ^x , -NHR ^x , -N Monovalent substituents such as (R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , -NHCOR ^x (R ^x is as described above).

The "substituent" in the "non-aromatic ring which may have a substituent" formed by R ^a and R ^b or two R ^a is not particularly limited, and examples thereof include halogen atoms, -NO ₂ , -CN, -COH, - OH, -SH, -NH ₂ , -COOH, -R ^x , -COR x , -OR ^x , -SR ^x , -SOR ^x , -SO ₂ R ^x , -NHR ^{x ,} -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , -NHCOR ^x , =O, etc. are monovalent substituents or divalent substituents (R ^x is as described above).

An aromatic ring refers to a ring that complies with Hückel's rule and the number of electrons contained in the π electron system on the ring is 4p+2 (p is a natural number). The aromatic ring may be an aromatic carbocyclic ring having only carbon atoms as ring constituent atoms, or an aromatic heterocyclic ring having as ring constituent atoms in addition to carbon atoms, heteroatoms such as oxygen atoms, nitrogen atoms, sulfur atoms, etc. The aromatic ring may be a monocyclic aromatic ring or a polycyclic aromatic ring. In one embodiment, the aromatic ring is preferably an aromatic ring with 5 to 14 members, more preferably an aromatic ring with 6 to 14 members, and even more preferably an aromatic ring with 6 to 10 members.

Examples of the "aromatic ring" in the "aromatic ring which may have a substituent" formed by two R ^a include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and the like.

In one embodiment, R ^a and R ^b are each independently preferably a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or an alkyl-substituted aromatic group. radical, aryl substituted by alkenyl, alkoxy, alkenyloxy, aryloxy, aralkyloxy, alkylcarbonyl, alkenylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylcarbonyloxy, Alkenylcarbonyloxy, arylcarbonyloxy, aralkylcarbonyloxy, alkoxycarbonyl, alkenyloxycarbonyl, aryloxycarbonyl, or aralkyloxycarbonyl; more preferably, a hydrogen atom, an alkyl group, Alkenyl, aryl, aralkyl, alkyl-substituted aryl, alkenyl-substituted aryl, alkoxy, alkenyloxy, aryloxy, or aralkoxy; more preferably, a hydrogen atom , alkyl, alkenyl, aryl, aralkyl, aryl substituted by alkyl, or aryl substituted by alkenyl; particularly preferably a hydrogen atom or an alkyl group.

R ^c each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent.

The "substituent" in the "alkyl group which may have a substituent" represented ^by R c and the "substituent" in the "alkenyl group which may have a substituent" represented by R ^c are not particularly limited, and examples thereof include halogen atoms. , -NO ₂ , -CN, -COH, -OH, -SH, -NH ₂ , -COOH, -R ^y , -COR ^x , -OR x , -SR ^x , -SOR ^{x ,} -SO ₂ R ^x , Monovalent substituents such as -NHR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , ^{-CONHR x} , -CON(R ^x ) ₂ , ^-NHCOR above).

R ^y can be selected from a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amine group, an aryl group, an aryl group substituted by an alkyl group, an aryl group substituted by an alkenyl group, an alkoxy group, an alkenyloxy group, and an aryloxy group. base, aralkyloxy, alkylcarbonyl, alkenylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, arylcarbonyloxy, aralkylcarbonyloxy, alkyl Oxycarbonyl, alkenyloxycarbonyl, aryloxycarbonyl, aralkyloxycarbonyl, alkylamino, di(alkyl)amine, alkenylamine, alkylalkenylamine, alkylcarbonylamino , alkenylcarbonylamino, alkylaminemethyl, and alkenylaminemethyl substituted aryl groups.

The "substituent" in the "aryl group which may have a substituent" represented by R ^c is not particularly limited, and examples thereof include halogen atoms, -NO ₂ , -CN, -COH, -OH, -SH, -NH ₂ , -COOH, -R ^x , -COR ^x , -OR ^x , -SR ^x , -SOR ^x , -SO ₂ R ^x , -NHR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , - Monovalent substituents such as CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , -NHCOR ^x (R ^x is as described above).

In one embodiment, R ^c is each independently preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an aryl group substituted by an alkyl group, or an aryl group substituted by an alkenyl group; particularly preferably is a hydrogen atom, or an alkyl group.

When R ¹ and R ² do not form a "non-aromatic ring that may have a substituent", formula (A):

[In the formula, each symbol is as above] In one embodiment, the partial structures shown are particularly preferably formulas (Ab1) to (Ab10):

[In the formula, each symbol is as above] Representation structure.

R each independently represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent.

The "substituent" in the "alkyl group which may have a substituent" represented by R and the "substituent" in the "alkenyl group which may have a substituent" represented by R are not particularly limited, and examples thereof include halogen atoms, - NO ₂ , -CN, -COH, -OH, -SH, -NH ₂ , -COOH, -R ^y , -COR ^x , -OR x , -SR ^x , -SOR ^{x ,} -SO ₂ R ^x , -NHR Monovalent substituents such as ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , -NHCOR ^x (R ^x and R ^y are As above).

The "substituent" in the "aryl group which may have a substituent" represented by R is not particularly limited, and examples include a halogen atom, -NO ₂ , -CN, -COH, -OH, -SH, -NH ₂ , - COOH, -R ^x , -COR ^x , -OR ^x , -SR ^x , -SOR ^x , -SO ₂ R ^x , -NHR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH _2. Monovalent substituents such as ^-CONHRx , -CON( ^Rx ) ₂ , ^-NHCORx ( ^Rx is as described above).

In one embodiment, R is each independently preferably (1) selected from halogen atoms, -NO ₂ , -CN, -COH, -OH, -NH ₂ , -COOH, -R ^y , -COR ^x , -OR ^x , -NHR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , and -NHCOR ^x are substituted by the base Alkyl group; (2) can be selected from halogen atoms, -NO ₂ , -CN, -COH, -OH, -NH ₂ , -COOH, -R ^y , -COR ^x , -OR ^x , -NHR ^x , - Alkenyl substituted by N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , and -NHCOR ^x ; or (3) may be selected from Halogen atom, -NO ₂ , -CN, -COH, -OH, -NH ₂ , -COOH, -R ^x , -COR ^x , -OR ^x , -NHR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , and -NHCOR ^x -substituted aryl groups (R ^x and R ^y are as described above).

In one embodiment, R is each independently preferably (1) and can be selected from -R ^y , -COR ^x , -OR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , - CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , and alkyl groups substituted by -NHCOR ^x ; (2) can be selected from -R ^y , -COR ^x , -OR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , and alkenyl substituted by -NHCOR ^x ; or (3) can be selected from -R ^x , Aryl groups substituted by -COR ^x , -OR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , and -NHCOR ^x (R ^x and R ^y are as above).

In an embodiment, R are independently and preferably (1) Aryl group that may be selected from (a) may be substituted with a group selected from alkyl, alkenyl, alkoxy, alkenyloxy, alkylcarbonyl, alkenylcarbonyl, and di(alkyl)amine groups , (b) alkoxy group, (c) alkenyloxy group, (d) alkylcarbonyl group, (e) alkenylcarbonyl group, (f) alkylcarbonyloxy group, (g) alkenylcarbonyloxy group, (h) Alkoxycarbonyl, (i) alkenyloxycarbonyl, (j) di(alkyl)amine, (k) alkylcarbonylamino, (l) alkenylcarbonylamino, (m) alkylaminemethane group, and (n) an alkyl group substituted by an alkenylamine carboxyl group; (2) Aryl group that may be selected from (a) may be substituted with a group selected from alkyl, alkenyl, alkoxy, alkenyloxy, alkylcarbonyl, alkenylcarbonyl, and di(alkyl)amine groups , (b) alkoxy group, (c) alkenyloxy group, (d) alkylcarbonyl group, (e) alkenylcarbonyl group, (f) alkylcarbonyloxy group, (g) alkenylcarbonyloxy group, (h) Alkoxycarbonyl, (i) alkenyloxycarbonyl, (j) di(alkyl)amine, (k) alkylcarbonylamino, (l) alkenylcarbonylamino, (m) alkylaminemethane group, and (n) an alkenyl group substituted by an alkenylamine carboxyl group; or (3) Aryl group which may be substituted by a group selected from (a) alkyl group and alkenyl group, (b) alkyl group, (c) alkenyl group, (d) alkoxy group, (e) alkenyl group group, (f) alkylcarbonyl group, (g) alkenylcarbonyl group, (h) alkylcarbonyloxy group, (i) alkenylcarbonyloxy group, (j) alkoxycarbonyl group, (k) alkenyloxycarbonyl group, (l) di(alkyl)amine group, (m) alkylcarbonylamino group, (n) alkenylcarbonylamino group, (o) alkylaminemethyl group, and (p) alkenylaminemethyl group substituted aryl group.

In one embodiment, R is each independently preferably (1) can be selected from (a) aryl, (b) alkoxy, (c) alkenyloxy, (d) alkylcarbonyl, (e) alkenylcarbonyl, (f) alkylcarbonyloxy, (g) alkenylcarbonyloxy, (h) alkoxycarbonyl, and (i) alkenyloxycarbonyl-substituted alkyl; (2) can be selected from (a) aryl, (b) alkoxy, (c) alkenyloxy, (d) alkylcarbonyl, (e) alkenylcarbonyl, (f) alkylcarbonyloxy, (g) alkenylcarbonyloxy, (h) alkoxycarbonyl, and (i) alkenyloxycarbonyl-substituted alkenyl; or (3) can be selected from (a) aryl, (b) alkyl, (c) alkenyl, (d) alkoxy, (e) alkenyloxy, (f) alkylcarbonyl, (g) alkenyl Aryl groups substituted with alkylcarbonyl, (h) alkylcarbonyloxy, (i) alkenylcarbonyloxy, (j) alkoxycarbonyl, and (k) alkenyloxycarbonyl.

Formula (A):

[In the formula, each symbol is as above] Specific examples of the partial structures shown are not particularly limited, and examples include formulas (A-1) to (A-437):

Representation structure.

R ³ and R ⁴ each independently represent a substituent.

The "substituent" represented by R ³ and R ⁴ is not particularly limited, and examples thereof include halogen atoms, -NO ₂ , -CN, -COH, -OH, -SH, -NH ₂ , -COOH, -R ^x , - COR ^x , -OR ^x , -SR ^x , -SOR ^x , -SO ₂ R ^x , -NHR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , - Monovalent substituents such as CON(R ^x ) ₂ and -NHCOR ^x (R ^x is as described above).

R ³ and R ⁴ , in one embodiment, are each independently preferably an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an aryl group substituted by an alkyl group, an aryl group substituted by an alkenyl group, or an alkoxy group. alkyl, alkenyloxy, aryloxy, or aralkoxy; more preferably, alkyl, alkenyl, aryl, aralkyl, alkyl-substituted aryl, or alkenyl-substituted aryl; and More preferably, it is an alkyl group; still more preferably, it is an alkyl group with more than 4 carbon atoms; still more preferably, it is an alkyl group with 4 to 14 carbon atoms; particularly preferably, it is a tert-butyl group.

Ring X ¹ and ring X ² each independently represent an aromatic carbocyclic ring which may have a substituent.

Aromatic carbocyclic rings refer to hydrocarbon rings that comply with Shocker's rule and the number of electrons contained in the π electron system on the ring is 4p+2 (p is a natural number). Aromatic carbocyclic rings are composed of only carbon atoms. The aromatic carbocyclic ring may be a monocyclic aromatic carbocyclic ring or a polycyclic condensed aromatic carbocyclic ring. In one embodiment, the aromatic carbocyclic ring is preferably an aromatic carbocyclic ring with 6 to 18 members, more preferably an aromatic carbocyclic ring with 6 to 14 members, and even more preferably an aromatic carbocyclic ring with 6 to 10 members. .

"Aromatic carbocyclic ring" represents "aromatic carbocyclic ring which may have a substituent" among ring ^X1 and ring ^X2 , and examples thereof include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc.

The "substituent" in the "aromatic carbocyclic ring which may have a substituent" representing Ring X ¹ and Ring X ² is not particularly limited, and examples thereof include halogen atoms, -NO ₂ , -CN, -COH, -OH, - SH, -NH ₂ , -COOH, -R ^x , -COR ^x , -OR ^x , -SR ^x , -SOR ^x , -SO ₂ R ^x , -NHR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , -NHCOR ^x and other monovalent substituents (R ^x is as described above).

In one embodiment, ring X ^{1 and} ring Alkenyl-substituted aryl, alkoxy, alkenyloxy, aryloxy, and aralkoxy-substituted benzene ring, or (2) may be selected from alkyl, alkenyl, aryl, aralkyl group, an aryl group substituted by an alkyl group, an aryl group substituted by an alkenyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, and a naphthalene ring substituted by an aralkyloxy group; more preferably, a naphthalene ring may be substituted by an alkyl group. base, alkenyl, aryl, aralkyl, alkyl-substituted aryl, alkenyl-substituted aryl, alkoxy, alkenyloxy, aryloxy, and aralkoxy-substituted benzene Ring; more preferably, it is a benzene ring that can be substituted by a group selected from alkyl, alkenyl, aryl, aralkyl, aryl substituted by alkyl, and aryl substituted by alkenyl; particularly preferably, it can be Alkyl-substituted benzene ring.

Y represents a single bond or organic group.

The organic group is not particularly limited. In one embodiment, for example, it is one or more (for example, 1 to 100, preferably 1 to 50, particularly preferably 1 to 50) selected from the group consisting of carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. A divalent group composed of 1 to 20 skeleton atoms. The non-skeleton atoms are composed of hydrogen atoms or halogen atoms. They can include linear structures, branched chain structures, and/or cyclic structures, and can contain no aromatic rings. The base may also be a base containing an aromatic ring. Examples of organic groups include -CR ^A R ^B -, -O-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO-, etc. (However, R ^A and R ^B represent each independently. A hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, R ^A and ^RB may also be bonded together to form a non-aromatic ring that may have a substituent).

a represents 0 or 1.

p and q respectively independently represent 0, 1, 2, 3 or 4; in one embodiment, preferably 0, 1, 2 or 3; more preferably 0, 1 or 2; even more preferably 0 or 1; The best value is 0.

Formula (B):

[In the formula, each symbol is as above] The partial structure shown is preferably formula (Ba) in one embodiment:

[In the formula, Y ¹ represents a single bond, -CR ^A R ^B -, -O-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO-; R ^A and R ^B are respectively Independently represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent. R ^A and R ^B may also be bonded together to form a non-aromatic ring that may have a substituent; R ⁵ and R ⁶ are Each independently represents a substituent; r and s each independently represent 0, 1, 2, 3 or 4; others are the structures represented by] as above; particularly preferably formula (Bb):

[In the formula, b means 0 or 1; Other symbols are as above] Representation structure.

Y ¹ represents a single bond, -CR ^A R ^B -, -O-, -S-, -SO-, -SO ₂ -, -CONH-, or -NHCO-; in one embodiment, it is preferably a single bond, -CR ^A R ^B -, or -O-; more preferably, it is a single bond, or -CR ^A R ^B -; particularly preferably -CR ^A R ^B -.

R ^A and R ^B independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent. R ^A and R ^B may also be bonded together to form a non-aromatic ring that may have a substituent. .

Suitable specific examples of the "non-aromatic ring" in the "non-aromatic ring which may have a substituent" formed by R ^A and R ^B include the "optional non-aromatic ring" formed by R ^a and R ^b or two R ^a Suitable specific examples of "non-aromatic ring" in "non-aromatic ring having a substituent" are the same as those listed.

The "substituent" in the "alkyl group which may have a substituent" represented by R ^A and R ^B is not particularly limited, and examples thereof include a halogen atom, -NO ₂ , -CN, -COH, -OH, -SH, - NH ₂ , -COOH, -R ^y , -COR ^x , -OR ^x , -SR ^x , -SOR ^x , -SO ₂ R ^x , -NHR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR Monovalent substituents such as ^x , _-CONH2 , ^-CONHRx , -CON( ^Rx ) ₂ , ^-NHCORx ( ^Rx and ^Ry are as described above).

The "substituent" in the "aryl group which may have a substituent" represented by R ^A and R ^B is not particularly limited, and examples thereof include a halogen atom, -NO ₂ , -CN, -COH, -OH, -SH, - NH ₂ , -COOH, -R ^x , -COR ^x , -OR ^x , -SR ^x , -SOR ^x , -SO ₂ R ^x , -NHR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR Monovalent substituents such as ^x , _-CONH2 , ^-CONHRx , -CON( ^Rx ) ₂ , ^-NHCORx ( ^Rx is as described above).

The "substituent" in the "optionally substituted non-aromatic ring" formed by R ^A and R ^B is not particularly limited, and examples thereof include halogen atoms, -NO ₂ , -CN, -COH, -OH, -SH, -NH ₂ , -COOH, -R ^x , -COR ^x , -OR ^x , -SR ^x , -SOR ^x , -SO ₂ R ^x , -NHR ^x , -N(R ^x ) ₂ , -COOR ^x , - OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , -NHCOR ^x , =O, etc. are monovalent substituents or divalent substituents (R ^x is as described above).

R ^A and R ^B , in one embodiment, each independently preferably represent (1) a hydrogen atom, (2) which may be selected from a halogen atom, an aryl group, an aryl group substituted by an alkyl group, or an alkenyl group. an alkyl group substituted by an aryl group, an alkoxy group, an alkenyl group, an aryloxy group, and an aralkyloxy group, or (3) may be selected from a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group group, an aryl group substituted by an alkyl group, an aryl group substituted by an alkenyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, and an aryl group substituted by an aralkyloxy group. R ^A and R ^B can also be used together. Bonded to form a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an aryl group substituted by an alkyl group, an aryl group substituted by an alkenyl group, an alkoxy group, an alkenyl group, an aryl group, Oxygen, aralkoxy, and non-aromatic rings substituted with pendant oxy groups.

^RA and R ^B , in one embodiment, each independently better represent (1) a hydrogen atom, or (2) an alkyl group that can be substituted by a halogen atom, ^RA and R ^B can also be bonded together, and Forming (A) a non-aromatic saturated carbocyclic ring with a monocyclic ring system that may be substituted with a group selected from an alkyl group and an aryl group, and (B) a non-aromatic saturated carbocyclic ring with a bicyclic ring system that may be substituted with a group selected from an alkyl group and an aryl group. An aromatic saturated carbocyclic ring, or (C) may be substituted with a group selected from an alkyl group and an aryl group, and a non-aromatic carbocyclic ring may be condensed with an aromatic ring (benzene ring, naphthalene ring, etc.) in a part.

^RA and R ^B , in one embodiment, are each independently and preferably represent a hydrogen atom or an alkyl group, and at least one of them is an alkyl group with 4 or more carbon atoms, or ^RA and R ^B are bonded together, It forms a non-aromatic saturated carbocyclic ring with a monocyclic ring system of 5 or more members (preferably 6 or more members) that can be substituted by an alkyl group, or a non-aromatic saturated carbocyclic ring with a bicyclic ring system of 6 or more members that can be substituted with an alkyl group. Saturated carbocyclic ring.

R ^A and R ^B , in one embodiment, are each independently and preferably represent a hydrogen atom or an alkyl group, and at least one of them is an alkyl group with 4 to 18 carbon atoms, or R ^A and R ^B are bonded together. Knot to form a non-aromatic saturated carbocyclic ring with a monocyclic ring system of 5 to 18 members (preferably 6 to 18 members) which may be substituted by an alkyl group having 1 to 6 carbon atoms.

In one embodiment ^{, RA and RB} are particularly preferably bonded together to form a cyclododecane ring.

R ⁵ and R ⁶ each independently represent a substituent.

The "substituent" represented by R ⁵ and R ⁶ is not particularly limited, and examples thereof include halogen atoms, -NO ₂ , -CN, -COH, -OH, -SH, -NH ₂ , -COOH, -R ^x , - COR ^x , -OR ^x , -SR ^x , -SOR ^x , -SO ₂ R ^x , -NHR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , - Monovalent substituents such as CON(R ^x ) ₂ and -NHCOR ^x (R ^x is as described above).

R ⁵ and R ⁶ , in one embodiment, are each independently preferably an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an aryl group substituted by an alkyl group, an aryl group substituted by an alkenyl group, or an alkoxy group. alkyl, alkenyloxy, aryloxy, or aralkoxy; more preferably, alkyl, alkenyl, aryl, aralkyl, alkyl-substituted aryl, or alkenyl-substituted aryl; and More preferably, it is an alkyl group; still more preferably, it is an alkyl group with more than 4 carbon atoms; still more preferably, it is an alkyl group with 4 to 18 carbon atoms; particularly preferably, it is a tert-butyl group.

R ⁵ and R ⁶ , in one embodiment, preferably at least one of R ⁵ and R ⁶ is an alkyl group with 4 or more carbon atoms; more preferably, at least one of R ⁵ and R ⁶ is an alkyl group with 4 carbon atoms ~18 alkyl group; particularly preferably, at least one of R ⁵ and R ⁶ is tert-butyl.

r and s respectively independently represent 0, 1, 2, 3 or 4; in one embodiment, preferably 0, 1, 2 or 3; more preferably 0, 1 or 2; even more preferably 0 or 1.

b represents 0 or 1; in one embodiment, 1 is preferred. Therefore, a represents 0, or a represents 1 and b represents 0 or 1; in one embodiment, it is preferable that a represents 0, or a represents 1 and b represents 1.

Formula (B):

[In the formula, each symbol is as above] Specific examples of the partial structures shown are not particularly limited, and may include formulas (B-1) to (B-41):

[In the formula, each symbol is as above] Representation structure.

In an embodiment when the partial structure represented by formula (B) is the structure represented by formula (Bb), it is preferred that R ¹ and R ² are independently hydrogen atoms, -CN, -NO ₂ , -COH, - R, -COR, or -COOR, R ¹ and R ² can also be bonded together to form a non-aromatic ring that may have a substituent; R are each independently (1) optionally selected from (a) optionally Aryl, (b) alkoxy, (c) alkenyloxy substituted from alkyl, alkenyl, alkoxy, alkenyloxy, alkylcarbonyl, alkenylcarbonyl, and di(alkyl)amine groups base, (d) alkylcarbonyl group, (e) alkenylcarbonyl group, (f) alkylcarbonyloxy group, (g) alkenylcarbonyloxy group, (h) alkoxycarbonyl group, (i) alkenyloxycarbonyl group, (j) di(alkyl)amine group, (k) alkylcarbonylamino group, (l) alkenylcarbonylamino group, (m) alkylaminemethyl group, and (n) alkenylaminemethyl group (2) may be selected from (a) may be selected from alkyl, alkenyl, alkoxy, alkenyloxy, alkylcarbonyl, alkenylcarbonyl, and di(alkyl)amine Aryl substituted with a group, (b) alkoxy, (c) alkenyloxy, (d) alkylcarbonyl, (e) alkenylcarbonyl, (f) alkylcarbonyloxy, (g) alkenylcarbonyl Oxygen group, (h) alkoxycarbonyl group, (i) alkenyloxycarbonyl group, (j) di(alkyl)amine group, (k) alkylcarbonylamino group, (l) alkenylcarbonylamino group, (m )alkylaminemethyl, and (n)alkenylaminemethyl substituted with a group selected from (a) alkenyl, and alkenyl; or (3) substituted with a group selected from (a) alkyl, and alkenyl Aryl, (b) alkyl, (c) alkenyl, (d) alkoxy, (e) alkenyloxy, (f) alkylcarbonyl, (g) alkenylcarbonyl, (h) alkylcarbonyloxy group, (i) alkenylcarbonyloxy group, (j) alkoxycarbonyl group, (k) alkenyloxycarbonyl group, (l) di(alkyl)amine group, (m) alkylcarbonylamino group, (n) Aryl groups substituted by alkenylcarbonylamino, (o)alkylaminemethyl, and (p)alkenylaminemethyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group. radical, alkenyl, aryl, aralkyl, alkyl-substituted aryl, alkenyl-substituted aryl, alkoxy, alkenyloxy, aryloxy, or aralkoxy; R ^A and R ^B represents independently (1) a hydrogen atom, (2) which may be selected from a halogen atom, an aryl group, an aryl group substituted by an alkyl group, an aryl group substituted by an alkenyl group, an alkoxy group, an alkenyloxy group, or an aryloxy group. group, and an alkyl group substituted by an aralkyloxy group, or (3) may be selected from a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an aryl group substituted by an alkyl group, an alkenyl group substituted Aryl groups substituted by aryl groups, alkoxy groups, alkenyloxy groups, aryloxy groups, and aralkoxy groups, R ^A and R ^B can also be bonded together to form a group that can be selected from a halogen atom, an alkyl group , alkenyl, aryl, aralkyl, aryl substituted by alkyl, aryl substituted by alkenyl, alkoxy, alkenyloxy, aryloxy, aralkyloxy, and pendant oxy groups Substituted non-aromatic ring; a and b independently represent 0 or 1; p, q, r and s independently represent 0, 1, 2, 3 or 4.

In an embodiment when the partial structure represented by formula (B) is the structure represented by formula (Bb), it is more preferred that R ¹ and R ² are each independently a hydrogen atom, -R, -COR, or -COOR, R ¹ and R ² can also be bonded together to form a non-aromatic ring that may have substituents; R are each independently (1) and can be selected from (a) aryl, (b) alkoxy, (c) Alkenyloxy, (d) alkylcarbonyl, (e) alkenylcarbonyl, (f) alkylcarbonyloxy, (g) alkenylcarbonyloxy, (h) alkoxycarbonyl, and (i) alkenyloxy An alkyl group substituted by a carbonyl group; (2) may be selected from (a) aryl, (b) alkoxy, (c) alkenyloxy, (d) alkylcarbonyl, (e) alkenylcarbonyl, Alkenyl substituted with (f) alkylcarbonyloxy, (g) alkenylcarbonyloxy, (h) alkoxycarbonyl, and (i) alkenyloxycarbonyl; or (3) may be selected from ( a) Aryl, (b) Alkyl, (c) Alkenyl, (d) Alkoxy, (e) Alkenyloxy, (f) Alkylcarbonyl, (g) Alkenylcarbonyl, (h) Alkyl Aryl groups substituted by carbonyloxy, (i) alkenylcarbonyloxy, (j) alkoxycarbonyl, and (k) alkenyloxycarbonyl; R ³ , R ⁴ , R ⁵ and R ⁶ are each independently is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an aryl group substituted by an alkyl group, or an aryl group substituted by an alkenyl group; R ^A and R ^B , in one embodiment, are each independently more preferably Represents (1) a hydrogen atom, or (2) an alkyl group which may be substituted by a halogen atom, R ^A and R ^B may also be bonded together to form (A) a single alkyl group which may be substituted by a group selected from an alkyl group and an aryl group. The non-aromatic saturated carbocyclic ring of the ring system, (B) the non-aromatic saturated carbocyclic ring of more than two rings that may be substituted by a group selected from alkyl and aryl groups, or (C) may be selected from alkyl and aryl groups. A non-aromatic carbocyclic ring substituted by a base and condensed with an aromatic ring (benzene ring or naphthalene ring, etc.) in part; a and b independently represent 0 or 1; p, q, r and s independently represent 0, 1, 2, 3 or 4.

In an embodiment in which the partial structure represented by formula (B) is a structure represented by formula (Bb), it is preferable that a is 0, s is 1 or more, and at least one of R ⁶ is an alkane having 4 or more carbon atoms. group; when a is 1 and b is 0, the total of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is an alkyl group with more than 4 carbon atoms; when a is 1 and b is 1, (1 ) the total of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is an alkyl group with more than 4 carbon atoms, and/or (2-1) R ^A and R ^B represent a hydrogen atom or an alkyl group, and At least one of them is an alkyl group with more than 4 carbon atoms, or (2-2) R ^A and R ^B are bonded together to form a monocyclic ring system with more than 5 members (preferably more than 6 members) that may be substituted by an alkyl group. A non-aromatic saturated carbocyclic ring, or a non-aromatic saturated carbocyclic ring with more than 6 members and a bicyclic ring system that may be substituted by an alkyl group.

In one embodiment when the partial structure represented by formula (B) is the structure represented by formula (Bb), it is more preferable that a is 0, s is 1 or more, and at least one of R ⁶ has a carbon number of 4 to 18. Alkyl group; when a is 1 and b is 0, the total of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is an alkyl group with 4 to 18 carbon atoms; when a is 1 and b is 1, (1) The total of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is an alkyl group with more than 4 carbon atoms, and/or (2-1) R ^A and R ^B represent a hydrogen atom or an alkyl group , and at least one of them is an alkyl group with 4 to 18 carbon atoms, or (2-2) R ^A and ^RB are bonded together to form an alkyl group with 5 to 18 carbon atoms (more Preferably, it is a non-aromatic saturated carbocyclic ring with a single ring system of 6 to 18 members.

In an embodiment in which the partial structure represented by formula (B) is the structure represented by formula (Bb), it is particularly preferred that a is 0, s is 1 or more, and at least one of R ⁶ is tert-butyl; a When a is 1 and b is 0, the total of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is tert-butyl; when a is 1 and b is 1, (1) The total of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is tert-butyl, and/or (2) R ^A and R ^B are bonded together to form a cyclododecane ring.

In one embodiment, the polyether resin of the present invention preferably has formula (1), in which the partial structure represented by formula (B) is the structure represented by formula (Ba):

[In the formula, each symbol is as above] Represents the repeating unit. The suitable range and specific examples of each structure in formula (2) are as described above.

In one embodiment, the polyether resin of the present invention is particularly preferably formula (3) in which the partial structure represented by formula (B) in formula (1) is the structure represented by formula (Bb):

[In the formula, each symbol is as above] Represents the repeating unit. The suitable range and specific examples of each structure in formula (3) are as described above.

In one embodiment, the polyether resin of the present invention preferably has formula (1), in which the partial structure represented by formula (A) is a structure represented by formulas (Aa1) to (Aa5) or (Ab1) to (Ab10). And the partial structure represented by formula (B) is the formula (4-1)~(4-30) of the structure represented by formula (Bb) (a is 0, or a is 1 and b is 1):

[In the formula, each symbol is as above] The repeating unit represented by any one of them. The suitable range and specific examples of each structure in formulas (4-1) to (4-30) are as explained above. In the polyether resin molecule of the present invention, formula (1) (more preferably formula (2), particularly preferably formula (3), most preferably a repeat of formula (4-1)~(4-30)) The mass ratio of units is preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 15 mass% or more, and particularly preferably 20 mass% or more.

The weight average molecular weight (Mw) of the polyether resin of the present invention is not particularly limited. In one embodiment, it is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more. The upper limit of the weight average molecular weight (Mw) of the polyether resin of the present invention is not particularly limited, but is preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 300,000 or less, and particularly preferably 200,000 or less. The weight average molecular weight of the polyether resin can be measured as a value converted to polystyrene by gel permeation chromatography (GPC).

The dielectric tangent (Df) of the polyether resin of the present invention is not particularly limited. When measured at 5.8 GHz and 23°C, in one embodiment, it is preferably 0.012 or less, more preferably 0.010 or less, and still more preferably 0.009. below, preferably below 0.008, further preferably below 0.007, and particularly preferably below 0.006. The dielectric tangent (Df) of the polyether resin can be measured as in Test Example A2 below.

The relative dielectric constant (Dk) of the polyether resin of the present invention is not particularly limited. When measured at 5.8 GHz and 23°C, in one embodiment, it is preferably 4.0 or less, more preferably 3.5 or less, and more preferably 3.5 or less. The best is 3.2 or less, the best is 3.0 or less, the best is 2.9 or less, and the best is 2.8 or less. The relative dielectric constant (Dk) of the polyether resin can be measured as in Test Example A2 below.

In one embodiment, the polyether resin of the present invention may be easily soluble in an organic solvent that can be used as a developer in the production of semiconductor packaging substrates. Examples of the organic solvent used as the developer include acetone, ethyl acetate, ethanol, isopropyl alcohol, butanol, methoxyethanol, ethoxyethanol, propoxyethanol, butoxyethanol, and diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, cyclohexanone, etc. The solubility of these organic solvents is not particularly limited, but may be 30% by mass or more at 100° C., for example.

The polyether resin of the present invention having a repeating unit represented by the formula (1), for example, can be obtained by reacting a polyether resin (PEEK) having a repeating unit represented by the following formula (1') so that Ph ₃ P=CR ¹ R ² [but each symbol is as above] represents Wittig's reagent (phosphorus ylide compound), or (R ^h O) ₂ (O=)P-CHR ¹ R ² [but R ^h is an alkane group, other symbols are as above] to produce a phosphonic acid diester compound represented by a reaction under alkaline conditions (Wittig reaction or Horner-Wadsworth-Emmons reaction).

In addition, the polyether resin of the present invention having a repeating unit represented by formula (1), when R ¹ and R ² in formula (1) are both -COR or -COOR or these together form a ring, can also be formed by PEEK having a repeating unit represented by the following formula (1') is produced by reacting a β-dicarbonyl compound represented by CH ₂ R ¹ R ² [but each symbol is as above] under alkaline conditions (Knoevenagel condensation reaction ).

In addition, the polyether resin of the present invention having a repeating unit represented by formula (1), when one of R ¹ and R ² in formula (1) is a hydrogen atom and the other is -COOR, can also be obtained by PEEK having a repeating unit represented by the following formula (1') is produced by reacting Meldrum's acid under alkaline conditions and then reacting an alcohol compound represented by R-OH (Knoevenagel condensation reaction).

[In the formula, each symbol is as above] As the above reaction conditions, the general reaction conditions of Wittig reaction, Horner-Wadsworth-Emmons reaction, or Knoevenagel condensation reaction can be directly used, or the reaction conditions thereof can be used mutatis mutandis. Examples of the base include piperazine and potassium carbonate. In addition, a solvent can also be used for the reaction. As a solvent, N-methylpyrrolidone, tetrahydrofuran, dimethyl ether, etc. can be used, for example. The reaction temperature can be appropriately set within the range of -80°C to 250°C. The reaction time can be in the range of 0.1 hours to 50 hours. In addition, after the reaction, it can be purified by a known method.

Furthermore, the above-mentioned reaction rate with respect to the structural unit represented by formula (1') may be less than 100 mol%, whereby the repeating unit represented by formula (1') can remain in the polyether resin of the present invention. Moreover, in one embodiment, the above-mentioned reaction rate with respect to the structural unit represented by formula (1') is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more. The best value may be 40 mol% or more. Therefore, in the polyether resin of the present invention, in one embodiment, the residual rate of the repeating unit represented by formula (1') is preferably less than 90 mol%, more preferably less than 80 mol%, and still more preferably The content may be less than 70 mol%, and preferably less than 60 mol%.

PEEK having a repeating unit represented by the following formula (1') can be obtained by using a difluoro compound or a dichloro compound represented by the following formula (1''-a), and the following formula (1''-b) The dihydroxy compound represented is produced by polymerization reaction under alkaline conditions.

[In the formula, Hal represents a fluorine atom or a chlorine atom independently, and other symbols are as above]. As the above-mentioned reaction conditions, general reaction conditions for polymerization reactions may be directly used or reaction conditions adapted therefrom may be used. Examples of the base include potassium carbonate and the like. In addition, a solvent can also be used for the reaction. As a solvent, N-methylpyrrolidone etc. can be used, for example. The reaction temperature can be appropriately set within the range of 100°C to 300°C. The reaction time can be in the range of 0.1 hours to 50 hours. In addition, after the reaction, it can be purified by a known method.

In addition, in the above-described production method, decarbonation reaction, deprotection reaction, oxidation reaction, reduction reaction, radical cyclization reaction, nucleophilic substitution reaction, alkylation reaction, halogenation reaction, condensation reaction, etc. may be further combined. A well-known reaction.

＜Resin composition＞ The resin composition of the present invention contains a curing crosslinking agent in addition to the polyether resin of the present invention. The curing crosslinking agent may be, for example, a compound having two or more polymerizable groups such as epoxy group, vinylphenyl group, isopropenylphenyl group, allyl group, acrylyl group, or methacryloyl group. The hardening cross-linking agent can be a component that hardens by self-polymerization or cross-links the hardening agent. Such a resin composition can be hardened by heating or light irradiation. Such a resin composition can have better dielectric properties in one embodiment.

The content of the polyether resin of the present invention in the resin composition of the present invention is not particularly limited. When the non-volatile component of the resin composition is 100 mass %, it is preferably 1 to 99 mass %, and more preferably 5 to 95 mass %. %, more preferably 10 to 90 mass %, still more preferably 15 to 90 mass %, still more preferably 30 to 95 mass %, and particularly preferably 50 to 90 mass %.

The curing cross-linking agent is preferably a photo-curing cross-linking agent. Therefore, in a suitable embodiment, the resin composition of the present invention contains a photocurable crosslinking agent and a photopolymerization initiator in addition to the polyether resin of the present invention. In this way, the resin composition can have better resolution.

The photocurable crosslinking agent may be, for example, a compound having two or more radically polymerizable groups such as vinylphenyl group, isopropenylphenyl group, allyl group, acrylyl group, and methacrylyl group. Examples of the photocurable cross-linking agent include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, and tricyclodecane di(meth)acrylate. Methanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate , 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylol Propane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glyceryl tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dioxanediol di(meth)acrylate ) acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate ) Acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-propenyloxyethoxy)phenyl]fluorine, Ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ginseng(3-hydroxypropyl)isocyanurate tri(meth)acrylate Poly(meth)acrylate compounds such as ester, (2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanurate tri(meth)acrylate, etc. wait. The photocurable cross-linking agent can be used alone or in combination of two or more types.

In the resin composition of the present invention, the content of the photocurable cross-linking agent is not particularly limited relative to the polyether resin of the present invention. It is preferably 3 to 25 parts by mass relative to 100 parts by mass of the polyether resin of the present invention. parts, preferably 5 to 20 parts by mass, and more preferably 8 to 15 parts by mass. The content of the photocurable cross-linking agent in the resin composition of the present invention is not particularly limited. When the non-volatile component of the resin composition is 100 mass %, it is preferably 1 to 20 mass %, and more preferably 3 to 15 mass %. , and more preferably 5~10% by mass.

Examples of photopolymerization initiators include α-aminoketone photopolymerization initiators, phosphine oxide photopolymerization initiators, α-hydroxyketone photopolymerization initiators, and oxime ester photopolymerization initiators. , benzoin-based photopolymerization initiator, benzyl ketal-based photopolymerization initiator, etc. The photopolymerization initiator preferably contains an oxime ester photopolymerization initiator.

Examples of the oxime ester photopolymerization initiator include 2-(benzyloxyimino)-1-[4-(phenylthio)phenyl]octane-1-one (OXE01), [1- [9-ethyl-6-(2-methylbenzyl)carbazol-3-yl]ethyleneamino]acetate (OXE02), etc.

Examples of phosphine oxide photopolymerization initiators include bis(2,4,6-trimethylbenzyl)phenylphosphine oxide and (2,4,6-trimethylbenzyl)diphenyl Phosphine oxide, polyoxyethylene glyceryl ether ginseng [phenyl (2,4,6-trimethylbenzyl) phosphinate] (Polymeric TPO-L), etc.

α-hydroxyketone photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl acetone, 1-[4-(2-hydroxyethoxy )phenyl]-2-hydroxy-2-methylacetone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropyl)benzyl]phenyl}-2-methyl Propan-1-one, etc.

Examples of benzoin-based photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. Examples of the benzyl ketal photopolymerization initiator include 2,2-dimethoxy-2-phenylacetophenone and the like.

α-Aminoketone photopolymerization initiator, for example, 2-methyl-1-phenyl-2-morpholinylpropan-1-one, 2-methyl-1-[4-(methylthio) )phenyl]-2-morpholinylpropan-1-one, 2-methyl-1-(4-hexylphenyl)-2-morpholinylpropan-1-one, 2-ethyl-2-( Dimethylamino)-1-(4-morpholinylphenyl)butan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinylphenyl) )butan-1-one, 2-(dimethylamino)-2-(4-methylphenylmethyl)-1-(4-morpholinylphenyl)butan-1-one, etc. The photopolymerization initiator may be used alone or in combination of two or more types.

In the resin composition of the present invention, the content of the photopolymerization initiator is not particularly limited relative to the polyether resin of the present invention. It is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the polyether resin of the present invention. parts, more preferably 0.5 to 5 parts by mass, and more preferably 1 to 3 parts by mass. The content of the photopolymerization initiator in the resin composition of the present invention is not particularly limited. When the non-volatile component of the resin composition is 100 mass%, it is preferably 0.1 to 10 mass%, and more preferably 0.5 to 5 mass%. , and more preferably 1 to 3% by mass.

The resin composition of the present invention preferably further contains a photosensitizer.

Photosensitizer, for example, preferably contains formula (5):

[In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, or an alkoxy group that may have a substituent] represents Photosensitizer.

The "substituent" in the "alkyl group which may have a substituent" and the "alkoxy group which may have a substituent" represented by R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ is not particularly limited, and examples thereof include Halogen atom, -NO ₂ , -CN, -COH, -OH, -SH, -NH ₂ , -COOH, -R ^y , -COR ^x , -OR ^x , -SR ^x , -SOR ^x , -SO ₂ R ^x , -NHR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ ^{, -NHCOR} and R ^y are as above).

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently preferably a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, or an alkoxy group; more preferably a hydrogen atom or a hydroxyl group; and more preferably R ¹¹ , R ¹² , R ¹⁴ and R ¹⁵ are hydrogen atoms and R ¹³ is a hydrogen atom or a hydroxyl group; particularly preferably, it is a hydrogen atom.

In the resin composition of the present invention, the content of the photosensitizer is not particularly limited relative to the polyether resin of the present invention. It is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the polyether resin of the present invention. , more preferably 0.5 to 17 parts by mass, and more preferably 1 to 15 parts by mass. The content of the photosensitizer in the resin composition of the present invention is not particularly limited. When the non-volatile component of the resin composition is 100 mass%, it is preferably 1 to 20 mass%, more preferably 3 to 15 mass%. More preferably, it is 5 to 10% by mass.

The resin composition of the present invention may further contain other additives. Examples of other additives include thermosetting resins such as epoxy resin and epoxy resin hardener; hardening accelerators; inorganic fillers such as silica; adhesion aids; fluorine-based surfactants and non-ionic interfaces Surfactants, cationic surfactants, anionic surfactants, polysiloxane surfactants, etc.; thermoplastic resins; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, oxidation Colorants for titanium, carbon black, naphthalene black, etc.; polymerization inhibitors for hydroquinone, phenothiazines, methylhydroquinone, hydroquinone monomethyl ether, catechol, gallic phenol, etc.; organic benton. , montmorillonite and other tackifiers; defoaming agents for polysilicone, fluorine and vinyl resins; epoxy resins, antimony compounds, phosphorus compounds, aromatic condensed phosphates, halogen-containing condensed phosphates, etc. Flame retardants, etc. For other additives, one type may be used alone or two or more types may be used in combination. The content of each component can be appropriately set by those with ordinary knowledge in the relevant technical field.

The resin composition of the present invention may further contain an organic solvent. Examples of organic solvents include ether solvents such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, anisole, dioxane, etc.; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. Glycol ether solvents such as methyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, etc.; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; cyclohexanone, cyclopentanone , ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; aliphatic hydrocarbons such as pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, and decalin Solvents; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, tetralin, etc.; methyl acetate, ethyl acetate, ethyl lactate, butyl lactate, γ-butyrolactone, methyl benzoate Ester-based solvents such as ester, α-acetyl-γ-butyrolactone, etc.; chlorine-based solvents such as chloroform, methylene chloride, 1,2-dichloroethane, etc.; nitrile-based solvents such as acetonitrile; N,N- Amide-based solvents such as dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.; styrene-based solvents such as dimethyl styrene, etc. The organic solvent can be used alone or in combination of two or more types.

The content of the organic solvent in the paint-like resin composition before drying is not particularly limited. It is preferably 100 to 5000 parts by mass, and more preferably 300 to 3000 parts by mass relative to 100 parts by mass of the polyether resin of the present invention. parts, preferably 500 to 1500 parts by mass.

The resin composition of the present invention can be obtained by properly mixing each component and, if necessary, using a kneading method such as a three-roller, ball mill, bead mill, sand mill, etc., or a super mixer, a planetary mixer, a high-speed rotary mixer, etc. It is produced by kneading or stirring with a stirring means such as a mixer.

The resin composition of the present invention can have excellent resolution. Therefore, in one embodiment, the resin composition of the present invention can have a smaller minimum opening diameter (minimum via hole diameter) of a via hole that can be formed during exposure and development. Therefore, in one embodiment, the minimum opening diameter when tested as in the following test example B1 is preferably 25 μm or less, more preferably 20 μm or less, still more preferably 18 μm or less, and still more preferably 15 μm. The thickness may be less than or equal to 12 μm, preferably less than 12 μm, and particularly preferably less than 10 μm.

The dielectric tangent (Df) of the cured product of the resin composition of the present invention is not particularly limited. When measured at 5.8 GHz and 23°C, in one embodiment, it is preferably 0.018 or less, 0.016 or less, 0.014 or less, or 0.012 or less. , better still is 0.010 or less, further better is 0.009 or less, still better is 0.008 or less, still better is 0.007 or less, and particularly best is 0.006 or less. The dielectric tangent (Df) of the cured product of the resin composition can be measured as in Test Example B2 below.

The relative dielectric constant (Dk) of the cured product of the resin composition of the present invention is not particularly limited. When measured at 5.8 GHz and 23°C, in one embodiment, it is preferably 4.0 or less, and more preferably 3.5 or less. , and even better can be less than 3.2, still better can be less than 3.0, still better can be less than 2.9, and particularly good can be less than 2.8. The relative dielectric constant (Dk) of the cured product of the resin composition can be measured as in Test Example B2 below.

The use of the resin composition of the present invention is not particularly limited and can be used in insulating resin sheets such as resin films and prepregs, insulating materials, silicon wafers, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists , buffer coating films, underfill materials, die bonding materials, semiconductor sealing materials, hole filling resins, parts embedding resins, etc. are widely used. Among them, resin compositions for insulating layers of printed wiring boards (printed wiring boards using a hardened product of a resin composition as an insulating layer) and resin compositions for interlayer insulating layers (a hardened product of a resin composition) can be suitably used. Printed wiring boards with interlayer insulating layers), resin compositions for plating (printed wiring boards with plating formed on hardened materials of the resin composition), and resin compositions for solder resists (resin compositions) Printed wiring boards in which the hardened material is a solder resist), resin compositions for rewiring forming layers in wafer level packaging (wafer level packaging in which the hardening material of the resin composition is used as a rewiring forming layer), fan-out wafers Resin composition for the rewiring forming layer of grade packaging (fan-out wafer level packaging using the hardened material of the resin composition as the rewiring forming layer), resin composition for the rewiring forming layer of fan-out panel level packaging ( Fan-out panel level packaging using the cured product of the resin composition as the rewiring formation layer), resin composition for buffer coating (semiconductor devices using the cured product of the resin composition as the buffer coating), and insulating layers for displays Resin composition (a display using the cured resin composition as an insulating layer).

Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition is also suitable as a resin composition for forming a rewiring forming layer that is an insulating layer for forming a rewiring layer. (resin composition for forming a rewiring formation layer), and a resin composition for sealing semiconductor wafers (resin composition for sealing semiconductor wafers). When manufacturing a semiconductor chip package, a rewiring layer may be further formed on the sealing layer. (1) The steps of laminating the temporary fixing film on the base material, (2) The steps of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) The step of forming a sealing layer on the semiconductor wafer, (4) The steps of peeling off the base material and temporary fixing film from the semiconductor wafer, (5) The step of forming a rewiring forming layer as an insulating layer on the surface of the peeled base material and temporary fixing film of the semiconductor wafer, and (6) The step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

The above-mentioned resin composition can also be used when the printed wiring board is a circuit board with built-in components.

＜Insulation Material＞ The insulating material of the present invention contains the polyether resin of the present invention.

＜Resin film＞ The resin film of the present invention has a support body and a resin composition layer formed of the resin composition of the present invention provided on the support body.

Examples of the support include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), and polycarbonate. (hereinafter sometimes referred to as "PC"), acrylic resins such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Ketones, polyimides, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are particularly preferred; polyethylene terephthalate film is especially preferred.

Moreover, metal foil can also be used as a support body. Examples of metal foil include copper foil, aluminum foil, and the like, and copper foil is preferred. As the copper foil, a foil composed of a single metal of copper or a foil composed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

Commercially available supports include, for example, product names "Alphan MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., product names "GF-1" and "GF-8" manufactured by Tamapoly Co., Ltd., and Shin-Etsu Film Co., Ltd. Polypropylene films manufactured by Teijin Co., Ltd., product name "PS-25" and other PS series polyethylene terephthalate films, etc., but are not limited to these.

Moreover, as a support body, the support body with a release layer which has a release layer on the surface which joins a resin composition layer can also be used. The release agent used for the release layer with the support of the release layer may be, for example, one selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and polysiloxane resin. The above release agent. Commercially available products can also be used as the support with the release layer. For example, "SK-1", a PET film having a release layer mainly composed of an alkyd resin release agent, manufactured by Lintec Corporation, can be used. "AL-5", "AL-7", "Lumirror T60" made by Toray, "Purex" made by Teijin, "Unipeel" made by Unitika, etc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Furthermore, when using a support with a release layer, it is preferable that the thickness of the entire support with a release layer is within the above range.

The thickness of the resin composition layer is not particularly limited, and may be, for example, 1 μm or more and 100 μm or less. Among them, 2 μm or more is particularly preferred, 4 μm or more is more preferred, 50 μm or less is more preferred, and 30 μm or less is more preferred.

The resin composition layer can also be protected by a protective film. By protecting the resin composition layer with a protective film, dust can be prevented from adhering to or scratching the surface of the resin composition layer. As the protective film, for example, a film made of the same material as the above-mentioned support body can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and still more preferably in the range of 10 μm to 30 μm. The protective film is preferably one in which the adhesive force between the resin composition layer and the protective film is smaller than the adhesive force between the resin composition layer and the support.

The resin film can be produced by, for example, applying a resin composition on a support using a die coater or the like, and drying the coating to form a resin composition layer if necessary.

Drying can be performed by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, but they are dried until the content of the organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it also depends on the boiling point of the organic solvent in the resin composition, for example, when using a resin composition containing 30% to 60% by mass of organic solvent, it can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes. Resin composition layer.

The resin film can be rolled into a roll shape and stored. When the resin film has a protective film, it can be used by peeling off the protective film.

＜Semiconductor package substrate＞ The semiconductor packaging substrate of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention. The insulating layer is preferably used as a rewiring formation layer, an interlayer insulating layer, a buffer coating film or a solder resist.

The semiconductor packaging substrate according to the first embodiment of the present invention can be manufactured using the resin composition according to the first embodiment of the present invention, and the cured product of the resin composition can be used as an insulating layer. Specifically, the manufacturing method of a semiconductor packaging substrate includes in order (I) The step of forming a resin composition layer made of the resin composition of the present invention on a circuit substrate, (II) The step of irradiating the resin composition layer with active light, and (III) The step of developing the resin composition layer.

＜Step (I)＞ Examples of methods for forming the resin composition layer include a method of directly applying a paint-like resin composition onto a circuit substrate and a method of using a resin film.

When the paint-like resin composition is directly applied to the circuit substrate, the organic solvent is volatilized by drying to form a resin composition layer on the circuit substrate.

Examples of the coating method of the resin composition include gravure coating, microgravure coating, reverse coating, reverse matching coating, die coating, slot die coating, and lip die coating. Notch wheel coating method, blade coating method, roller coating method, knife coating method, curtain coating method, chamber gravure coating method, slit method, spin coating method cloth method, slit coating method, spray coating method, dip coating method, hot melt coating method, rod coating method, applicator method, air knife coating method, curtain flow coating method flow coating) method, offset printing method, brush coating method, full-surface printing method using screen printing method, etc.

The resin composition can be applied several times or once, or it can be applied by combining different methods in plural. Among them, the die coating method with excellent uniform coating properties is particularly preferred. In addition, in order to avoid contamination of foreign matter, etc., it is preferable to perform the coating step in an environment such as a clean room where foreign matter is rarely generated.

After the resin composition is coated, it is dried in a hot air oven or far infrared oven as needed. The preferred drying conditions are 80℃~120℃, 3 minutes to 13 minutes. In this way, a resin composition layer is formed on the circuit substrate.

Examples of the circuit substrate include a glass epoxy resin substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, here, the circuit board refers to a board in which a patterned conductor layer (circuit) is formed on one or both sides of the above-mentioned supporting board. In addition, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, the substrate of the conductor layer (circuit) that is patterned on one or both sides of the outermost layer of the multilayer printed wiring board also includes In what is called a circuit substrate here. Furthermore, the surface of the conductor layer may also be blackened or roughened in advance by copper etching.

On the other hand, when using a resin film, the resin composition layer side is laminated on one or both sides of the circuit board using a vacuum laminating machine. In the lamination step, if the resin film has a protective film, the protective film is removed, the resin film and the circuit substrate are preheated as necessary, and the resin composition layer is pressure-bonded to the circuit substrate while being pressurized and heated. Among the resin films, a method of laminating it on a circuit board under reduced pressure by a vacuum lamination method can be suitably used.

The conditions for lamination are not particularly limited. For example, the crimping temperature (lamination temperature) is preferably 70°C to 140°C and the crimping pressure is preferably 1kgf/cm ² to 11kgf/cm ² (9.8×10 ⁴ N/m ² ~107.9×10 ⁴ N/m ² ), the crimping time is preferably set to 5 seconds to 300 seconds, and the air pressure is set to 20mmHg (26.7hPa) or less for lamination under reduced pressure. In addition, the lamination step may be a batch type or a continuous type using a roller. The vacuum lamination method can be performed using a commercially available vacuum lamination machine. Commercially available vacuum laminators include, for example, a vacuum coater manufactured by Nikko-Materials, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roller dry coater manufactured by Hitachi Industries, and a vacuum coater manufactured by Hitachi AIC. Laminating machine, etc.

<Step (II)> After the resin composition layer is provided on the circuit substrate, an exposure step is performed in which specific parts of the resin composition layer are irradiated with active light through the mask pattern. Examples of active rays include ultraviolet rays, visible rays, electron beams, X-rays, etc., and ultraviolet rays are particularly preferred. The amount of ultraviolet irradiation is approximately 10mJ/cm ² ~1000mJ/cm ² . The exposure method can be either a contact exposure method in which the mask pattern is closely adhered to the circuit board, or a non-contact exposure method in which parallel light is used to expose without close contact.

In step (II), as the mask pattern, for example, a through hole pattern such as a round hole pattern can be used to form through holes. The through hole diameter (opening diameter) is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less. The lower limit is not particularly limited, and may be 0.1 μm or more, 0.5 μm or more, etc.

＜Step (III)＞ After the exposure step, a pattern can be formed by performing a development step in which the unexposed portions of the resin composition layer are removed with a developer. Development is usually performed by wet development.

In the above-mentioned wet development, a safe, stable and operable developer such as an alkaline solution, an aqueous developer, an organic solvent, etc. can be used as the developer. In addition, as the development method, known methods such as spraying, shaking dipping, brushing, and scraping can be suitably used.

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

In order to improve the development effect, these alkaline aqueous solutions may contain surfactants, defoaming agents, etc. The pH of the above-mentioned alkaline aqueous solution is, for example, preferably in the range of 8 to 12, more preferably in the range of 9 to 11. In addition, the alkali concentration of the above-mentioned alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the above-mentioned alkaline aqueous solution can be appropriately selected according to the developability of the resin composition layer, and is preferably 20°C to 50°C.

Organic solvents used as the developer include, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group with 1 to 4 carbon atoms, ethanol, isopropyl alcohol, butanol, and diethylene glycol monomethyl ether. , diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, cyclohexanone.

The concentration of the organic solvent is preferably 2 mass% to 90 mass% relative to the total amount of the developer. In addition, the temperature of the organic solvent can be adjusted according to the developability. Furthermore, such organic solvents may be used alone or in combination of two or more. Examples of organic solvent-based developers used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, and methylisobutyl base ketone, γ-butyrolactone.

When forming patterns, more than two developing methods can be used in combination as needed. The development methods include immersion method, liquid coating method, spray method, high-pressure spray method, brush, scraping, etc. For the purpose of improving resolution, high-pressure spray method is suitable. The spray pressure when using the spray method is preferably 0.05MPa~0.3MPa.

＜Thermal hardening (post-baking) step＞ After the above step (III) is completed, the thermal hardening (post-baking) step is performed as necessary. The resin composition layer may be hardened in the above steps (I) to (III), but the resin composition may be further hardened through the thermal hardening step to obtain an insulating layer with excellent mechanical strength. Post-baking steps can include heating steps using a clean oven, etc. The environment during thermal hardening can be in the air or in an inert gas environment such as nitrogen. In addition, the heating conditions can be appropriately selected according to the type and content of the resin components in the resin composition. Preferably, the heating conditions are in the range of 150°C to 250°C and 20 minutes to 180 minutes, and more preferably in the range of 160°C to 230°C. Choose from the range of 30 minutes to 120 minutes.

＜Other steps＞ The manufacturing method of the semiconductor packaging substrate may further include a hole opening step and a smear removal step after forming the insulating layer as the hardened resin composition layer. These steps may be implemented in accordance with various methods known to those skilled in the art for manufacturing semiconductor packaging substrates.

After the insulating layer is formed, a hole opening step is performed on the insulating layer formed on the circuit substrate as desired to form a through hole or a through hole. The hole opening step can be performed, for example, by well-known methods such as drills, lasers, plasmas, etc., or by combining these methods as needed. Preferably, drilling is performed by lasers such as carbonic acid gas laser, YAG laser, etc. hole steps.

The desmearing step is a step for desmearing. Generally, resin residue (smear) adheres to the inside of the opening formed in the hole drilling step. Such smear may cause poor electrical connections, so a smear removal process (smear removal process) is performed in this step.

The desmearing treatment can be carried out by dry desmearing treatment, wet desmearing treatment or a combination thereof.

Dry desmear treatment, for example, uses plasma to remove desmear. The desmear treatment using plasma can be carried out using a commercially available plasma desmear treatment device. Among commercially available plasma desmear treatment devices, examples suitable for manufacturing semiconductor packaging substrates include a microwave plasma device manufactured by Nissin Corporation, an atmospheric pressure plasma etching device manufactured by Sekisui Chemical Industry Co., Ltd., etc. .

Wet desmearing treatment includes, for example, desmearing treatment using an oxidizing agent solution. When an oxidant solution is used for desmearing, it is preferred to perform swelling treatment with a swelling solution, oxidation treatment with an oxidant solution, and neutralization treatment with a neutralizing solution in this order. Examples of the swelling liquid include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing the substrate on which through holes are formed in a swelling liquid heated to 60°C to 80°C for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganic acid aqueous solution, for example, a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution. The oxidation treatment with an oxidizing agent solution is preferably performed by immersing the swelling-treated substrate in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Examples of commercially available alkaline permanganic acid aqueous solutions include "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. The neutralization treatment with a neutralizing solution is preferably performed by immersing the oxidized substrate in a neutralizing solution at 30°C to 50°C for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and an example of a commercially available product is "Reduction Solution Securiganth P" manufactured by Atotech Japan.

When a combination of dry desmearing and wet desmearing is performed, the dry desmearing may be performed first or the wet desmearing may be performed first.

When the insulating layer is formed as any one of a rewiring formation layer, an interlayer insulating layer, and a solder resist, the hole opening step and the desmearing step may be performed after the thermal hardening step. In addition, in the method of manufacturing a semiconductor package substrate, a plating step may be further performed.

The plating step is a step of forming a conductor layer on the insulating layer. As for the conductor layer, it can be formed by sputtering after the insulating layer is formed. It can also be formed by combining electroless plating and electrolytic plating. In addition, a plating resist with a pattern opposite to that of the conductor layer can also be formed. agent, only electroless plating is used to form the conductor layer. As a subsequent pattern forming method, for example, a subtractive method, a semi-additive method, etc., which are well known to those skilled in the art, can be used.

The semiconductor package substrate according to the second embodiment of the present invention can be manufactured using the above-mentioned resin composition, and a cured product of the resin composition can be used as a rewiring formation layer. Specifically, the manufacturing method of semiconductor packaging substrate includes (A) The steps of laminating the temporary fixing film on the base material, (B) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (C) The step of forming a sealing layer on the semiconductor wafer, (D) The step of peeling off the base material and the temporary fixing film from the semiconductor wafer, (E) The step of forming a rewiring formation layer as an insulating layer on the surface of the peeled base material and temporary fixing film of the semiconductor wafer, (F) The step of forming a rewiring layer as a conductor layer on the rewiring formation layer, and (G) The step of forming a solder resist layer on the rewiring layer. In addition, the aforementioned manufacturing method of semiconductor chip packaging may also include (H) A step of packaging a plurality of semiconductor wafers, cutting them into individual semiconductor wafer packages, and singulating them into individual wafers.

<Step (A)> Step (A) is a step of laminating a temporary fixing film on a base material. The lamination conditions of the base material and the temporary fixing film are not particularly limited. For example, the crimping temperature (lamination temperature) is preferably 70°C to 140°C, and the crimping pressure is preferably 1kgf/cm ² to 11kgf /cm ² , the crimping time is preferably set to 5 seconds to 300 seconds, and the air pressure is set to 20mmHg or less for lamination under reduced pressure. In addition, the lamination step may be a batch type or a continuous type using a roller. The vacuum lamination method can be performed using a commercially available vacuum lamination machine. Commercially available vacuum laminators include, for example, a vacuum coater manufactured by Nikko-Materials, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roller dry coater manufactured by Hitachi Industries, and a vacuum coater manufactured by Hitachi AIC. Laminating machine, etc.

Examples of substrates include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel plates (SPCC); FR-4 substrates, etc., in which glass fiber is infiltrated with epoxy resin and heated Hardened substrate; substrate composed of bismaleimidetriazine resin such as BT resin, etc.

The temporary fixing film can use any material that can be peeled off from the semiconductor wafer and can temporarily fix the semiconductor wafer. Examples of commercially available products include "Revalpha" manufactured by Nitto Denko Co., Ltd.

＜Step (B)＞ Step (B) is a step of temporarily fixing the semiconductor wafer on the temporary fixing film. The semiconductor chip can be temporarily fixed using devices such as flip-chip bonders and die bonders, for example. The layout and number of arrangements of semiconductor wafers can be appropriately set according to the shape and size of the temporary fixing film, the target production number of semiconductor packages, etc. For example, the semiconductor wafers can be arranged in a matrix with a plurality of rows and a plurality of columns for temporary fixation.

＜Step (C)＞ Step (C) is a step of forming a sealing layer on the semiconductor wafer. The sealing layer may be made of any insulating material, or the resin composition of the present invention may be used. The sealing layer is usually formed by a method including a step of forming a sealing resin composition layer on a semiconductor wafer, and a step of thermally or photocuring the resin composition layer to form the sealing layer.

The sealing resin composition layer is preferably formed by compression molding. In the compression molding method, a semiconductor wafer and a sealing resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the sealing resin composition in the mold to form a sealing resin composition layer covering the semiconductor wafer.

Specific operations of the compression molding method can be performed as follows, for example. Prepare the upper mold and lower mold as molds for compression molding. Furthermore, the sealing resin composition is applied to the semiconductor wafer temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the sealing resin composition is mounted on the lower mold together with the base material and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped, and heat and pressure are applied to the sealing resin composition to perform compression molding.

Moreover, the specific operation of the compression molding method can also be performed as follows, for example. Prepare the upper mold and lower mold as molds for compression molding. The sealing resin composition is placed on the lower mold. Furthermore, the semiconductor wafer is mounted on the upper mold together with the base material and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped so that the sealing resin composition placed on the lower mold is adjacent to the semiconductor wafer mounted on the upper mold, and heat and pressure are applied to perform compression molding.

Molding conditions vary depending on the composition of the sealing resin composition, and appropriate conditions can be adopted to achieve good sealing. For example, the temperature of the mold during molding is preferably a temperature at which the sealing resin composition can exhibit excellent compression moldability. It is preferably 80°C or higher, more preferably 100°C or higher, and particularly preferably 120°C or higher; preferably 200°C or lower, more preferably 170°C or lower, particularly preferably 150°C or lower. Moreover, the pressure applied during molding is preferably 1 MPa or more, more preferably 3 MPa or more, particularly preferably 5 MPa or more; preferably 50 MPa or less, more preferably 30 MPa or less, and particularly preferably 20 MPa or less. The hardening time is preferably 1 minute or more, more preferably 2 minutes or more, and particularly preferably 5 minutes or more; it is preferably 60 minutes or less, more preferably 30 minutes or less, and particularly preferably 20 minutes or less. Usually, after the sealing resin composition layer is formed, the mold is removed. The mold may be removed before or after thermal hardening of the sealing resin composition layer.

The compression molding method can also be performed by discharging the sealing resin composition filled in the box out of the lower mold.

＜Step (D)＞ Step (D) is a step of peeling off the base material and the temporary fixing film from the semiconductor wafer. The peeling method is preferably a method appropriate to the material of the temporary fixation film. Examples of the peeling method include a method of peeling off the temporarily fixed film by heating, foaming or expanding it. An example of the peeling method is a method of irradiating the temporarily fixed film with ultraviolet rays through the base material to reduce the adhesive force of the temporarily fixed film and peeling it off.

In the method of heating, foaming or expanding the temporarily fixed film to peel off, the heating conditions are usually 100°C to 250°C for 1 second to 90 seconds or 5 minutes to 15 minutes. In addition, in the method of irradiating ultraviolet rays to reduce the adhesive force of the temporarily fixed film and peeling it off, the amount of ultraviolet irradiation is usually 10mJ/cm ² ~ 1000mJ/cm ² .

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

When forming the rewiring formation layer, in order to connect the semiconductor chip and the rewiring layer between layers, a through hole may also be formed in the rewiring formation layer.

The through hole can usually be removed by performing an exposure step of irradiating active light rays through a mask pattern on the surface of the resin composition layer used to form the rewiring formation layer, and developing the non-exposed portion that is not irradiated with active light rays. formed by steps. The irradiation amount and irradiation time of the active light can be appropriately set according to the resin composition layer. Exposure methods include, for example, the contact exposure method that exposes the mask pattern in close contact with the resin composition layer, the non-contact exposure method that uses parallel light to expose the mask pattern without closely contacting the resin composition layer, etc. . The active light, alkali aqueous solution, and exposure and development methods are as described above.

The shape of the through hole is not particularly limited, but is generally circular (substantially circular). The top diameter of the through hole is preferably 50 μm or less, more preferably 30 μm or less, and more preferably 20 μm or less; preferably 0.1 μm or more, preferably 0.5 μm or more, and more preferably 1.0 μm or more. Here, the diameter of the top of the through hole refers to the diameter of the opening of the through hole on the surface of the rewiring formation layer.

＜Step (F)＞ Step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring formation layer. The method of forming the rewiring layer on the rewiring formation layer may be the same as the method of forming the conductor layer on the insulating layer in the first embodiment. Alternatively, steps (E) and (F) may be repeated to alternately stack the rewiring layers and the rewiring formation layers (layer build-up).

＜Step (G)＞ Step (G) is a step of forming a solder resist layer on the rewiring layer. The material of the solder resist layer can be any insulating material. Among them, photosensitive resins and thermosetting resins are particularly preferred from the viewpoint of easy manufacturing of semiconductor chip packages. In addition, the resin composition of the present invention can also be used.

In addition, in step (G), bump processing to form bumps may also be performed as needed. Bump processing can be performed by solder balls, plating soldering, etc. In addition, the formation of the through hole in the bump processing can be performed in the same manner as step (E).

The manufacturing method of semiconductor chip packaging may also include step (H) in addition to steps (A) to (G). Step (H) is a step of cutting a plurality of semiconductor chip packages into individual semiconductor chip packages for singulation. The method of cutting the semiconductor wafer package into individual semiconductor wafer packages is not particularly limited.

＜Semiconductor Device＞ The semiconductor device of the present invention includes the semiconductor chip package of the present invention. Semiconductor devices equipped with semiconductor chip packages include, for example, electrical products (such as computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions, etc.) and vehicles ( For example, various semiconductor devices used in motorcycles, automobiles, trains, ships, aircraft, etc.). [Example]

The present invention will be specifically described below through examples, but the present invention is not limited to these examples. In addition, in the following description, "parts" and "%" indicating amounts mean "mass parts" and "mass %" respectively, unless otherwise stated. The temperature condition when there is no special temperature specified is room temperature (23℃), and the pressure condition when there is no special pressure specified is atmospheric pressure (1atm). The weight average molecular weight is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography.

<Comparative Example A1: Synthesis of polyether resin (A)>

Place 21.8g of 4,4'-difluorobenzophenone, 11.0g of hydroquinone, and 15.1g of potassium carbonate into a detachable flask with a capacity of 500 mL, add 150 mL of N-methyl-2-pyrrolidone, and infuse under nitrogen and stir at room temperature for 30 minutes. Heat to 185°C and polymerize for 3 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, it was dried under vacuum drying at 80° C. to obtain 28 g of polyether resin (A). The molecular weight of the polyether resin (A) was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight average molecular weight (Mw) was 80,000.

<Example A1: Synthesis of polyether resin (1)>

Dissolve 31.8g of the polyether resin (A) obtained in Comparative Example A1, 15.1g of potassium carbonate, and 12.4g of dimethylmethylphosphonate in 150 mL of N-methylpyrrolidone, heat it to 180°C, and stir for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, it was dried under vacuum drying at 80° C. to obtain 25 g of polyether resin (1). When the molecular weight of the polyether resin (1) was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 80,000.

IR (cm ^-1 ): 2937, 2862, 2370, 2325, 1657, 1593, 1498, 1472, 1444, 1415, 1306, 1278, 1241, 1160, 1112, 1068, 1014, 929, 874, 85 0,767,725 , 687, 598, 553, 528

<Example A2: Synthesis of polyether resin (2)>

Dissolve 31.8g of polyether resin (A) obtained in Comparative Example A1, 15.1g of potassium carbonate, and 22.8g of diethyl benzyl phosphonate in 150 mL of N-methylpyrrolidone, heat to 180°C, and stir for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, it was dried under vacuum drying at 80° C. to obtain 30 g of polyether resin (2).

<Example A3: Synthesis of polyether resin (3)>

Dissolve 31.8g of polyether resin (A) obtained in Comparative Example A1, 15.1g of potassium carbonate, and 16.6g of dimethyl (2-side oxypropyl) phosphonate in 150 mL of N-methylpyrrolidone, and heat Stir until it reaches 180°C for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, it was dried under vacuum drying at 80° C. to obtain 25 g of polyether resin (3).

<Example A4: Synthesis of polyether resin (4)>

Dissolve 31.8g of polyether resin (A) obtained in Comparative Example A1, 15.1g of potassium carbonate, and 16.6g of trimethylphosphonoacetate in 150 mL of N-methylpyrrolidone, heat to 180°C, and stir 5 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, the polymer was dried under vacuum drying at 80° C. to obtain 29 g of polyether resin (4).

<Example A5: Synthesis of polyether resin (5)>

Dissolve 31.8g of the polyether resin (A) obtained in Comparative Example A1, 15.1g of potassium carbonate, 0.43g of piperazine, and 13.2g of dimethyl malonate in 150 mL of N-methylpyrrolidone, and heat it to 140°C. , stir for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, the polymer was dried under vacuum drying at 80° C. to obtain 28 g of polyether resin (5).

<Test Example A1: Solubility Test> The polyether resin produced in each Example and Comparative Example was added to cyclopentanone in an amount of 30% by mass, and heated at 100° C. for 1 hour. Those that were completely dissolved were evaluated as "O", and those that were not completely dissolved were evaluated as "×".

<Test Example A2: Measurement of relative dielectric constant (Dk) and dielectric tangent (Df)> The polyether resin produced in each Example and Comparative Example was added to N-methylpyrrolidone so that it would become 10 mass %, and it heated at 100 degreeC for 1 hour. Next, the dried resin layer was applied on the release surface of the polyethylene terephthalate film (PET film, "AL-5" manufactured by Lindec Co., Ltd., thickness 38 μm) that had been treated with alkyd release. Use a die coater to evenly apply the dissolved polymer so that the thickness becomes 20 μm, dry at 80~110°C (average 95°C) for 5 minutes, and heat at 180°C for 2 hours. By using the PET film as a support Peel off to produce a cured film.

Cut a test piece with a width of 2 mm and a length of 80 mm from the cured film. For the cut out test piece, the relative dielectric constant (Dk) was measured using the measuring device "HP8362B" manufactured by Agilent Technologies using the resonant cavity perturbation method at a measuring frequency of 5.8 GHz and a measuring temperature of 23°C. and dielectric tangent (Df).

The measurement results and evaluation results of Test Examples A1 and A2 performed on the polyether resins obtained in Examples A1 to A5 and Comparative Example A1 are shown in Table 1 below.

<Reference Example A1: Synthesis of polyether resin (B)>

Place 21.8g of 4,4'-difluorobenzophenone, 16.6g of t-butylhydroquinone, and 15.1g of potassium carbonate into a detachable flask with a capacity of 500 mL, and add N-methyl-2-pyrrolidone 150 mL, stirred at room temperature for 30 minutes under nitrogen. Heat to 185°C and polymerize for 3 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, it was dried under vacuum drying at 80° C. to obtain 35 g of polyether resin (B). When the molecular weight of the polyether resin (B) was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 150,000.

<Example A6: Synthesis of polyether resin (6)>

Dissolve 37.4g of polyether resin (B) obtained in Reference Example A1, 15.1g of potassium carbonate, and 16.6g of dimethyl (2-side oxypropyl) phosphonate in 150 mL of N-methylpyrrolidone, and heat Stir until it reaches 180°C for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, the polymer was dried under vacuum drying at 80° C. to obtain 31 g of polyether resin (6).

<Example A7: Synthesis of polyether resin (7)>

Dissolve 37.4g of polyether resin (B) obtained in Reference Example A1, 15.1g of potassium carbonate, and 22.4g of diethylmethylphosphonate in 150 mL of N-methylpyrrolidone, heat to 180°C, and stir for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, it was dried under vacuum drying at 80° C. to obtain 25 g of polyether resin (7).

<Example A8: Synthesis of polyether resin (8)>

Dissolve 37.4g of polyether resin (B) obtained in Reference Example A1, 15.1g of potassium carbonate, and 16.6g of triethylphosphonoacetate in 150 mL of N-methylpyrrolidone, heat to 180°C, and stir 5 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, the polymer was dried under vacuum drying at 80° C. to obtain 32 g of polyether resin (8). When the molecular weight of the polyether resin (8) was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 90,000.

IR (cm ^-1 ): 2925, 2849, 2353, 2028, 1652, 1592, 1496, 1471, 1415, 1305, 1277, 1238, 1159, 1065, 1013, 927, 873, 837, 766, 724, 597, 553

<Example A9: Synthesis of polyether resin (9)>

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, and 14.4 g of Melvin's acid were dissolved in 150 mL of N-methylpyrrolidone, and the mixture was heated to 60° C. and stirred for 8 hours. 7.4 g of t-butanol was added and stirred at 130°C for 2 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, it was dried under vacuum drying at 80° C. to obtain 35 g of polyether resin (9).

<Example A10: Synthesis of polyether resin (10)>

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, and 14.4 g of Melvin's acid were dissolved in 150 mL of N-methylpyrrolidone, and the mixture was heated to 60° C. and stirred for 8 hours. 11.6 g of hydroxyethyl acrylate was added, and the mixture was stirred at 130° C. for 2 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, it was dried under vacuum drying at 80° C. to obtain 37 g of polyether resin (10). When the molecular weight of the polyether resin (10) was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 80,000.

IR (cm ^-1 ): 2929, 2848, 1723, 1650, 1591, 1496, 1471, 1415, 1367, 1305, 1277, 1238, 1159, 1062, 1034, 1013, 927, 873, 836, 766 , 684, 597 , 553, 503, 429

<Example A11: Synthesis of polyether resin (11)>

Dissolve 37.4g of the polyether resin (B) obtained in Reference Example A1, 15.1g of potassium carbonate, 0.43g of piperazine, and 13.2g of dimethyl malonate in 150 mL of N-methylpyrrolidone, and heat it to 140°C. , stir for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, it was dried under vacuum drying at 80° C. to obtain 38 g of polyether resin (11).

<Example A12: Synthesis of polyether resin (12)>

Dissolve 37.4g of polyether resin (B) obtained in Reference Example A1, 15.1g of potassium carbonate, 0.43g of piperazine, and 15.6g of diethyl malonate in 150 mL of N-methylpyrrolidone, and heat it to 140°C. , stir for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, it was dried under vacuum drying at 80° C. to obtain 38 g of polyether resin (12).

<Example A13: Synthesis of polyether resin (13)>

Dissolve 37.4g of polyether resin (B) obtained in Reference Example A1, 15.1g of potassium carbonate, 0.43g of piperazine, and 20.5g of dit-butyl malonate in 150 mL of N-methylpyrrolidone, and heat until it becomes 140°C, stir for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, the polymer was dried under vacuum drying at 80° C. to obtain 38 g of polyether resin (13).

<Example A14: Synthesis of polyether resin (14)>

Dissolve 37.4g of the polyether resin (B) obtained in Reference Example A1, 15.1g of potassium carbonate, 0.43g of piperazine, and 10.0g of acetylacetone in 150 mL of N-methylpyrrolidone, heat to 140°C, and stir 5 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, it was dried under vacuum drying at 80° C. to obtain 38 g of polyether resin (14).

<Example A15: Synthesis of polyether resin (15)>

37.4g of polyether resin (B) obtained in Reference Example A1, 15.1g of potassium carbonate, 0.43g of piperazine, and 13.8g of 5,5-dimethyl-1,3-cyclohexanedione (dimedone) were dissolved in N- 150 mL of methylpyrrolidone, heated to 140°C, and stirred for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, it was dried under vacuum drying at 80° C. to obtain 39 g of polyether resin (15).

<Example A16: Synthesis of polyether resin (16)>

37.4 g of the polyether resin (B) obtained in Reference Example A1, 0.43 g of piperazine, and 14.4 g of Melic acid were dissolved in 150 mL of N-methylpyrrolidone, heated to 60°C, and stirred for 10 hours. Next, the obtained reaction liquid was dropped into 2 L of acetone to precipitate the polymer for purification. After filtering off the purified polymer, it was dried under vacuum drying at 40° C. to obtain 39 g of polyether resin (16).

<Example A17: Synthesis of polyether resin (17)>

Dissolve 37.4g of the polyether resin (B) obtained in Reference Example A1, 15.1g of potassium carbonate, 0.43g of piperazine, and 12.8g of ethyl acetyl acetate in 150 mL of N-methylpyrrolidone, and heat it to 140°C. Stir for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of acetone to precipitate the polymer for purification. After filtering off the purified polymer, it was dried under vacuum drying at 40° C. to obtain 35 g of polyether resin (17).

<Example A18: Synthesis of polyether resin (18)>

Dissolve 37.4g of polyether resin (B) obtained in Reference Example A1, 15.1g of potassium carbonate, 0.43g of piperazine, and 15.6g of t-butyl acetoacetate in 150 mL of N-methylpyrrolidone, and heat to 140 ℃, stir for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of acetone to precipitate the polymer for purification. After filtering off the purified polymer, it was dried under vacuum drying at 40° C. to obtain 37 g of polyether resin (18).

<Example A19: Synthesis of polyether resin (19)>

Dissolve 37.4g of polyether resin (B) obtained in Reference Example A1, 15.1g of potassium carbonate, 0.43g of piperazine, and 21.4g of ethylene glycol monoacetyl acetate monomethacrylate in N-methylpyrrolidone. 150 mL, heated to 140°C, and stirred for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of acetone to precipitate the polymer for purification. After filtering off the purified polymer, the polymer was dried under vacuum drying at 40° C. to obtain 42 g of polyether resin (19). The molecular weight of the polyether resin (19) was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight average molecular weight (Mw) was 100,000.

IR (cm ^-1 ): 3303, 2948, 1650, 1593, 1497, 1462, 1415, 1385, 1365, 1307, 1279, 1241, 1160, 1113, 1058, 1014, 966, 929, 874, 842 , 768, 698 , 607, 587, 563, 530

The measurement results and evaluation results of Test Examples A1 and A2 performed on the polyether resins obtained in Examples A6 to A19 and Reference Example A1 are shown in Tables 2 and 3 below.

<Reference Example A2: Synthesis of polyether resin (C)>

Place 21.8g of 4,4'-difluorobenzophenone, 35.5g of BisP-CDE (bisphenol body, manufactured by Honshu Chemical Co., Ltd.), and 15.1g of potassium carbonate into a detachable flask with a capacity of 500 mL, and add N-methyl 150 mL of methyl-2-pyrrolidinone, stirred at room temperature for 30 minutes under nitrogen. Heat to 185°C and polymerize for 3 hours. Next, the obtained reaction liquid was dropped into 2 L of ultrapure water, and the polymer was precipitated for purification. After filtering off the purified polymer, the polymer was dried under vacuum drying at 80° C. to obtain 52 g of polyether resin (C). When the molecular weight of the polyether resin (C) was measured by gel permeation chromatography (in terms of standard polystyrene), the weight average molecular weight (Mw) was 180,000.

IR (cm ^-1 ): 2932, 2861, 1651, 1592, 1497, 1472, 1444, 1415, 1346, 1305, 1278, 1239, 1160, 1114, 1067, 1036, 1013, 964, 928, 87 3,849,766 , 725, 684, 598, 563

<Example A20: Synthesis of polyether resin (20)>

Dissolve 56.0g of the polyether resin (C) obtained in Reference Example A2, 15.1g of potassium carbonate, 0.43g of piperazine, and 21.4g of ethylene glycol monoacetyl acetate monomethacrylate in N-methylpyrrolidone. 150 mL, heated to 140°C, and stirred for 5 hours. Next, the obtained reaction liquid was dropped into 2 L of acetone to precipitate the polymer for purification. After filtering off the purified polymer, it was dried under vacuum drying at 40° C. to obtain 58 g of polyether resin (20). The molecular weight of the polyether resin (20) was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight average molecular weight (Mw) was 50,000.

IR (cm ^-1 ): 2933, 2862, 1726, 1651, 1592, 1496, 1472, 1445, 1415, 1367, 1307, 1278, 1238, 1159, 1143, 1067, 1014, 953, 928, 87 3,837,766 , 726, 683, 597, 553, 526, 500, 429, 420, 410

The measurement results and evaluation results of Test Examples A1 and A2 performed on the polyether resin obtained in Example A20 and Reference Example A2 are shown in Table 4 below.

<Example B1> 100 parts by mass of the polyether resin (4) obtained in Example A4, 16 parts by mass of a photocurable cross-linking agent (trimethylolpropane tri(meth)acrylate), and an oxime ester photopolymerization initiator (BASF Corporation Preparation of "Irgacure-OXE02", 2 parts by mass of [1-[9-ethyl-6-(2-methylbenzyl)carbazol-3-yl]ethyleneamino]acetate, photoincreased 4 parts by mass of sensitizer (1-phenyl-5-mercapto-1H-tetrazole, photosensitizer represented by the following formula (5')) was dissolved in 900 parts by mass of N-methylpyrrolidone to prepare a resin composition things.

<Example B2> The resin composition was prepared in the same manner as in Example B1 except that the same amount of the polyether resin (8) obtained in Example A8 was used instead of the polyether resin (4) obtained in Example A4.

<Example B3> The resin composition was prepared in the same manner as in Example B1 except that the polyether resin (10) obtained in Example A10 was used in place of the polyether resin (4) obtained in Example A4.

<Example B4> The resin composition was prepared in the same manner as in Example B1, except that the polyether resin (16) obtained in Example A16 was used in place of the polyether resin (4) obtained in Example A4.

<Example B5> The resin composition was prepared in the same manner as in Example B1 except that the same amount of the polyether resin (17) obtained in Example A17 was used instead of the polyether resin (4) obtained in Example A4.

<Comparative example B1> The resin composition was prepared in the same manner as in Example B1 except that the polyether resin (A) obtained in Comparative Example A1 was used in the same amount in place of the polyether resin (4) obtained in Example A4.

<Reference example B1> The resin composition was prepared in the same manner as in Example B1 except that the polyether resin (B) obtained in Reference Example A1 was used in place of the polyether resin (4) obtained in Example A4.

<Reference example B2> The resin composition was prepared in the same manner as in Example B1 except that the polyether resin (C) obtained in Reference Example A2 was used in the same amount in place of the polyether resin (4) obtained in Example A4.

<Test example B1: Evaluation of ultimate resolution (resolution)> The resin compositions obtained in Examples B1 to B5, Comparative Example B1, and Reference Examples B1 and B2 were laminated and plated with copper on a silicon wafer with a film thickness of 10 μm, and then roughened in a 1% hydrochloric acid aqueous solution for 10 seconds. On the substrate, apply a spin coater at a rotation number suitable for a film thickness of 10 μm, and then heat on a hot plate at 120° C. for 5 minutes to prepare a resin composition layer. Call it a laminate.

The produced laminate was exposed to ultraviolet light (wavelength: 365 nm, intensity: 40 mW/cm ² ). The exposure amount is set to the optimal value in the range from 50mJ/ ^cm2 to 1000mJ/ ^cm2 . The exposure pattern uses a quartz glass mask depicting round holes (through holes) with openings of 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 25 μm, and 30 μm.

Next, the entire surface of the resin composition layer on the laminate was spray developed using cyclopentanone as a developer at a spray pressure of 0.2 MPa and an optimal time between 30 seconds and 300 seconds. Next, acetic acid 2 -Methoxy-1-methylethyl ester (PGMEA) was sprayed and rinsed with a spray pressure of 0.2MPa for 30 seconds. Further, heat treatment was performed at 180° C. for 120 minutes to harden the resin composition layer.

The diameters of the bottoms of the through holes with openings of 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 25 μm, and 30 μm in the exposure pattern of the hardened resin composition layer were observed with SEM (magnification: 1000 times) and measured. The smallest size that can be opened is used as the ultimate resolution.

<Test example B2: Measurement of relative dielectric constant (Dk) and dielectric tangent (Df)> The resin compositions obtained in Examples B1 to B5, Comparative Example B1, and Reference Examples B1 and B2 were placed on an alkyd release-treated polyethylene terephthalate film (PET film, manufactured by Lintec Co., Ltd. On the release surface of "AL-5", thickness 38 μm), apply the resin composition layer evenly with a die coater so that the thickness of the dried resin composition layer becomes 20 μm. The resin composition on the PET film was dried at 80 to 110°C (average 95°C) for 5 minutes, heated at 180°C for 2 hours, and the PET film was peeled off to produce a cured film.

A test piece with a width of 2 mm and a length of 80 mm is cut from the hardened film. For the cut out test piece, the relative dielectric constant (Dk) was measured using the measuring device "HP8362B" manufactured by Agilent Technologies using the resonant cavity perturbation method at a measuring frequency of 5.8 GHz and a measuring temperature of 23°C. and dielectric tangent (Df).

Table 5 below shows the content of each component in the resin compositions prepared in Examples B1 to B5, Comparative Example B1, and Reference Examples B1 and B2, and the measurement results of Test Examples B1 and B2.

This case is based on Special Application No. 2022-028105 (application date: February 25, 2022) filed with the Japan Patent Office, and all its contents are included in this specification.

Claims (13)

A polyether resin having formula (1): [In the formula, R ¹ and R ² independently represent a hydrogen atom, -CN, -NO ₂ , -COH, -R, -OR, -COR, -COOR, -CONHR, -CONR ₂ , -SR, -SOR , or -SO ₂ R, R ¹ and R ² can also be bonded together to form a non-aromatic ring that may have a substituent; R each independently represents an alkyl group that may have a substituent, or an alkenyl group that may have a substituent, or an aryl group that may have a substituent; R ³ and R ⁴ each independently represent a substituent; Ring X ¹ and Ring X ² each independently represent an aromatic carbocyclic ring that may have a substituent; Y represents a single bond or an organic group; a represents 0 or 1; p and q are repeating units that independently represent 0, 1, 2, 3 or 4]. Such as the polyether resin of claim 1, which has formula (3): [In the formula, R ¹ and R ² independently represent a hydrogen atom, -R, -COR, or -COOR. R ¹ and R ² can also be bonded together to form a non-aromatic ring that may have a substituent; R is Each independently represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent; R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a substituent; R ^A and R ^B independently represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent. R ^A and R ^B may also be bonded together to form a non-aromatic ring that may have a substituent; a and b represent 0 or 1 independently; p, q, r and s represent repeating units representing 0, 1, 2, 3 or 4 respectively. For example, the polyether resin of claim 2, when a is 0, s is 1 or more, and at least one of R ⁶ is an alkyl group with a carbon number of 4 or more; when a is 1 and b is 0, the total of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is an alkyl group with more than 4 carbon atoms; when a is 1 and b is 1, (1) the total of r and s is 1 or more, and R ⁵ and R ⁶ At least one of them is an alkyl group with more than 4 carbon atoms, and/or (2-1) R ^A and R ^B represent a hydrogen atom or an alkyl group, and at least one of them is an alkyl group with more than 4 carbon atoms, or (2- 2) R ^A and R ^B are bonded together to form a non-aromatic saturated carbocyclic ring with a monocyclic ring system of more than 5 members that can be substituted by an alkyl group, or a bicyclic ring system with more than 6 members that can be substituted by an alkyl group. Non-aromatic saturated carbocyclic ring. For example, the polyether resin of claim 1 has a weight average molecular weight of more than 5,000. For example, the polyether resin of Claim 1 has a dielectric tangent (Df) of 0.012 or less when measured at 5.8 GHz and 23°C. An insulating material containing the polyether resin of claim 1. A resin composition containing the polyether resin of claim 1 and a curing cross-linking agent. A resin composition containing the polyether resin of claim 1, a photocurable crosslinking agent, and a photopolymerization initiator. The resin composition of claim 8 further contains a photosensitizer. A resin sheet having a support body and a resin composition layer formed of the resin composition according to any one of claims 7 to 9 provided on the support body. A semiconductor packaging substrate, which includes an insulating layer formed by a cured product of the resin composition according to any one of claims 7 to 9. A semiconductor device including the semiconductor packaging substrate of claim 11. A method for manufacturing a semiconductor packaging substrate, which includes the following steps (I)~(III) in sequence; (I) The step of forming a resin composition layer formed of the resin composition of claim 8 or 9 on a circuit substrate, (II) The step of irradiating the resin composition layer with active light, (III) The step of developing the resin composition layer.