WO2023163111A1

WO2023163111A1 - Polyether resin

Info

Publication number: WO2023163111A1
Application number: PCT/JP2023/006758
Authority: WO
Inventors: 将毅長嶋
Original assignee: 味の素株式会社
Priority date: 2022-02-25
Filing date: 2023-02-24
Publication date: 2023-08-31
Also published as: JPWO2023163111A1; TW202342587A

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 and have finer wiring in order to make electronic devices smaller and more functional.

As a manufacturing technology for printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by thermosetting or photocuring a resin composition. As such a resin composition, for example, the resin composition disclosed in Patent Document 1 is known.

JP 2019-66792 A

In recent years, with the increase in communication speed and capacity in communication equipment, the resin used in the manufacture of semiconductor package substrates for communication equipment is required to have a lower dielectric loss tangent, that is, to have better dielectric properties. Further, in order to ensure further precision, resin compositions used for manufacturing semiconductor package substrates are required to have better resolution.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a resin having excellent dielectric properties. Another object of the present invention is to provide a resin composition having better resolution.

As a result of diligent studies, the inventors of the present invention newly discovered a polyether resin with excellent dielectric properties and completed the present invention. They also found that a resin composition using such a polyether resin has better resolution.

That is, the present invention includes the following contents.
[1] Formula (1):

[In the formula,
R ¹ and R ² each independently represent a hydrogen atom, —CN, —NO ₂ , —COH, —R, —OR, —COR, —COOR, —CONHR, —CONR ₂ , —SR, —SOR, or —SO ₂ R, wherein R ¹ and R ² may combine together to form a non-aromatic ring which may have a substituent;
R each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
R ³ and R ⁴ each independently represent a substituent;
Ring X ¹ and Ring X ² each independently represent an aromatic carbocyclic ring which may have a substituent;
Y represents a single bond or an organic group;
a represents 0 or 1;
p and q each independently represent 0, 1, 2, 3, or 4; ]
Polyether resin having a repeating unit represented by.
[2] Formula (3):

[In the formula,
R ¹ and R ² each independently represent a hydrogen atom, —R, —COR, or —COOR, and R ¹ and R ² are bonded together to form an optionally substituted non- may form an aromatic ring;
R each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a substituent;
^RA and ^RB ^{each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, and RA and RB} ^together may be combined to form a non-aromatic ring optionally having a substituent;
a and b each independently represent 0 or 1;
p, q, r and s each independently represent 0, 1, 2, 3 or 4; ]
The polyether resin according to [1] above, which has a repeating unit represented by:
[3] if a is 0,
s is 1 or more, and at least one of R ⁶ is an alkyl group having 4 or more carbon atoms;
If a is 1 and b is 0,
the sum of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is an alkyl group having 4 or more carbon atoms;
If a is 1 and b is 1,
(1) the sum of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is an alkyl group having 4 or more carbon atoms, and/or (2-1) R ^A and R ^B are represents a hydrogen atom or an alkyl group, and at least one of which is an alkyl group having 4 or more carbon atoms, or (2-2) R ^A and R ^B are bonded together and substituted with an alkyl group Forming a 5-membered or more monocyclic non-aromatic saturated carbocyclic ring that may be optionally substituted with an alkyl group, or a 6-membered or more bicyclic or higher non-aromatic saturated carbocyclic ring that may be substituted with an alkyl group [2] Polyether resin according to .
[4] The polyether resin according to any one of [1] to [3] above, which has a weight average molecular weight of 5,000 or more.
[5] The polyether resin according to any one of [1] to [4] above, which has a dielectric loss tangent (Df) of 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 [1] to [5] above.
[7] A resin composition comprising the polyether resin according to any one of [1] to [5] above and a curable cross-linking agent.
[8] A resin composition comprising the polyether resin according to any one of [1] to [5] above, a photocurable cross-linking agent, and a photopolymerization initiator.
[9] The resin composition according to [8] above, further comprising a photosensitizer.
[10] A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of [7] to [9] provided on the support.
[11] A semiconductor package substrate comprising an insulating layer formed from a cured product of the resin composition according to any one of [7] to [9] above.
[12] A semiconductor device including the semiconductor package substrate according to [11] above.
[13] A method for manufacturing a semiconductor package substrate including the following steps (I) to (III) in this order.
(I) Step of forming a resin composition layer formed of the resin composition according to [8] or [9] above on a circuit board (II) Step of irradiating the resin composition layer with actinic rays (III) ) Step of developing the resin composition layer

According to the present invention, it is possible to provide a polyether resin with excellent dielectric properties. Also, a resin composition having better resolution can be provided.

The present invention will be described in detail below in accordance with its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and equivalents thereof.

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

[In the formula,
R ¹ and R ² each independently represent a hydrogen atom, —CN, —NO ₂ , —COH, —R, —OR, —COR, —COOR, —CONHR, —CONR ₂ , —SR, —SOR, or —SO ₂ R, wherein R ¹ and R ² may combine together to form a non-aromatic ring which may have a substituent;
R each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
R ³ and R ⁴ each independently represent a substituent;
Ring X ¹ and Ring X ² each independently represent an aromatic carbocyclic ring which may have a substituent;
Y represents a single bond or an organic group;
a represents 0 or 1;
p and q each independently represent 0, 1, 2, 3, or 4; ]
It has a repeating unit represented by Such polyether resins have 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 each independently represent a hydrogen atom, —CN, —NO ₂ , —COH, —R, —OR, —COR, —COOR, —CONHR, —CONR ₂ , —SR, —SOR, or —SO ₂ R, and R ¹ and R ² may combine together to form a non-aromatic ring which may have a substituent.

R ¹ and R ² are, in one embodiment, preferably each independently a hydrogen atom, —CN, —NO ₂ , —COH, —R, —COR, —COOR, —CONHR, or —CONR ₂ and R ¹ and R ² may be joined together to form an optionally substituted non-aromatic ring.

In one embodiment, R ¹ and R ² are more preferably each independently a hydrogen atom, —CN, —NO ₂ , —COH, —R, —COR, or —COOR, and R ¹ and R ² may be bonded together to form a non-aromatic ring which may have a substituent.

R ¹ and R ² are, in one embodiment, more preferably each independently a hydrogen atom, —R, —COR, or —COOR, and R ¹ and R ² are bonded together and substituted It may form a non-aromatic ring which may have a group.

In one embodiment, R ¹ and R ² are particularly preferably each independently a hydrogen atom, —COR, or —COOR, and R ¹ and R ² are bonded together and have a substituent. may form an optional non-aromatic ring.

The “substituent” in the “optionally substituted non-aromatic ring” formed by R ¹ and R ² is not particularly limited, but examples include 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 , —CONHR ^x , —CON(R ^x ) ₂ , —NHCOR ^x , ═O and other monovalent or divalent substituents. be done.

R ^x each independently represents (1) a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an aryl group, an alkyl-substituted aryl group, an alkenyl-substituted aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group; , aralkyloxy group, alkylcarbonyl group, alkenylcarbonyl group, arylcarbonyl group, aralkylcarbonyl group, alkylcarbonyloxy group, alkenylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group, alkyloxycarbonyl group, alkenyloxycarbonyl group , an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkylamino group, a di(alkyl)amino group, an alkenylamino group, an alkylalkenylamino group, an alkylcarbonylamino group, an alkenylcarbonylamino group, an alkylcarbamoyl group, and an alkenylcarbamoyl group Alkyl group optionally substituted with a selected group; (2) Halogen atom, nitro group, cyano group, hydroxy group, amino group, aryl group, alkyl-substituted aryl group, alkenyl-substituted aryl group, alkoxy group, alkenyloxy group , aryloxy group, aralkyloxy group, alkylcarbonyl group, alkenylcarbonyl group, arylcarbonyl group, aralkylcarbonyl group, alkylcarbonyloxy group, alkenylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group, alkyloxycarbonyl group, alkenyloxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylamino group, di(alkyl)amino group, alkenylamino group, alkylalkenylamino group, alkylcarbonylamino group, alkenylcarbonylamino group, alkylcarbamoyl group, and alkenyl group optionally substituted with a group selected from alkenylcarbamoyl group; or (3) halogen atom, nitro group, cyano group, hydroxy group, amino group, alkyl group, alkenyl group, aryl group, aralkyl group, alkyl substitution aryl group, alkenyl-substituted aryl group, alkoxy group, alkenyloxy group, aryloxy group, aralkyloxy group, alkylcarbonyl group, alkenylcarbonyl group, arylcarbonyl group, aralkylcarbonyl group, alkylcarbonyloxy group, alkenylcarbonyloxy group, aryl carbonyloxy group, aralkylcarbonyloxy group, alkyloxycarbonyl group, alkenyloxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylamino group, di(alkyl)amino group, alkenylamino group, alkylalkenylamino group, alkyl It is an aryl group optionally substituted with a group selected from a carbonylamino group, an alkenylcarbonylamino group, an alkylcarbamoyl group and an alkenylcarbamoyl group.

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

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

An alkenyl group means a linear, branched and/or cyclic monovalent unsaturated aliphatic hydrocarbon group having at least one carbon-carbon double bond. The number of carbon atoms in the alkenyl group is preferably 2 to 18, more preferably 2 to 10, even more preferably 2 to 6, unless otherwise specified. The alkenyl group includes, for example, vinyl group, propenyl group (allyl group, 1-propenyl group, isopropenyl group), butenyl group (1-butenyl group, crotyl group, methallyl group, isocrotyl group, etc.), pentenyl group (1- pentenyl group, etc.), hexenyl group (1-hexenyl group, etc.), heptenyl group (1-heptenyl group, etc.), octenyl group (1-octenyl group, etc.), cyclopentenyl group (2-cyclopentenyl group, etc.), cyclohexenyl group (3-cyclohexenyl group, etc.) and the like.

An aryl group means a monovalent aromatic hydrocarbon group from which one hydrogen atom is removed from an aromatic carbocyclic ring. The number of carbon atoms in the aryl group is preferably 6-18, particularly preferably 6-10, unless otherwise specified. Examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group and the like.

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

An alkyl-substituted aryl group means an aryl group substituted with one or more alkyl groups. The number of carbon atoms in the alkyl-substituted aryl group is preferably 7-19, particularly preferably 7-11, unless otherwise specified. Examples of alkyl-substituted aryl groups include 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethyl phenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group and the like.

An alkenyl-substituted aryl group means an aryl group substituted with one or more alkenyl groups. The number of carbon atoms in the alkenyl-substituted aryl group is preferably 8-20, particularly preferably 8-12, unless otherwise specified. Examples of alkenyl-substituted aryl groups include 4-vinylphenyl group, 3-vinylphenyl group, 2-vinylphenyl group, 2,4-divinylphenyl group, 3,5-divinylphenyl group, 4-isopropenylphenyl group, 3-isopropenylphenyl group, 2-isopropenylphenyl group, 4-allylphenyl group and the like.

An alkoxy group means a monovalent 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)). The number of carbon atoms in the alkoxy group is preferably 1 to 18, more preferably 1 to 10, even more preferably 1 to 6, unless otherwise specified. Examples of alkoxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, isobutyloxy, sec-butyloxy and tert-butyloxy groups.

An 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)). The number of carbon atoms in the alkenyloxy group is preferably 2 to 18, more preferably 2 to 10, even more preferably 2 to 6, unless otherwise specified. The alkenyloxy group includes, for example, a vinyloxy group and a propenyloxy group (allyloxy group, 1-propenyloxy group, isopropenyloxy group) and the like.

An 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)). The number of carbon atoms in the aryloxy group is preferably 6-18, particularly preferably 6-10, unless otherwise specified. The aryloxy group includes, for example, a phenoxy group, a 1-naphthoxy group, a 2-naphthoxy group and the like.

An aralkyloxy 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)). The number of carbon atoms in the aralkyloxy group is preferably 7-19, particularly preferably 7-11, unless otherwise specified. The aralkyloxy group includes, for example, benzyloxy group, α-methylbenzyloxy group and the like.

An 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)). The number of carbon atoms in the alkylcarbonyl group is preferably 2 to 19, more preferably 2 to 11, even more preferably 2 to 7, unless otherwise specified. Examples of alkylcarbonyl groups include acetyl group, propanoyl group, butanoyl group and the like.

An alkenylcarbonyl group means a monovalent group in which an alkenyl group is bonded to one side of a carbonyl group (that is, a group represented by R ^s2 -C(=O)-(R ^s2 is an alkenyl group)). The number of carbon atoms in the alkenylcarbonyl group is preferably 3-19, more preferably 3-11, even more preferably 3-7, unless otherwise specified. The alkenylcarbonyl group includes, for example, a vinylcarbonyl group and a propenylcarbonyl group (allylcarbonyl group, 1-propenylcarbonyl group, isopropenylcarbonyl group) and the like.

An arylcarbonyl group means a monovalent group in which an aryl group is bonded to one side of a carbonyl group (that is, a group represented by R ^s3 -C(=O)-(R ^s3 is an aryl group)). The number of carbon atoms in the arylcarbonyl group is preferably 7-19, particularly preferably 7-11, unless otherwise specified. The arylcarbonyl group includes, for example, benzoyl group, 1-naphthoyl group, 2-naphthoyl group and the like.

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

An 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)). do. The number of carbon atoms in the alkylcarbonyloxy group is preferably 2 to 19, more preferably 2 to 11, even more preferably 2 to 7, unless otherwise specified. The alkylcarbonyloxy group includes, for example, an acetyloxy group, a propanoyloxy group, a butanoyloxy group and the like.

An 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)). do. The number of carbon atoms in the alkenylcarbonyloxy group is preferably 3 to 19, more preferably 3 to 11, even more preferably 3 to 7, unless otherwise specified. The alkenylcarbonyloxy group includes, for example, vinylcarbonyloxy group, propenylcarbonyloxy group (allylcarbonyloxy group, 1-propenylcarbonyloxy group, isopropenylcarbonyloxy group) and the like.

An 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)). do. The number of carbon atoms in the arylcarbonyloxy group is preferably 7-19, particularly preferably 7-11, unless otherwise specified. The arylcarbonyloxy group includes, for example, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group and the like.

An 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)). do. The number of carbon atoms in the aralkylcarbonyl group is preferably 7-19, particularly preferably 7-11, unless otherwise specified. The aralkylcarbonyloxy group includes, for example, a benzylcarbonyloxy group, an α-methylbenzylcarbonyloxy group and the like.

An alkoxycarbonyl group means a monovalent group in which an alkoxy group is bonded to one side of a carbonyl group (that is, a group represented by R ^s1 -OC(=O)-(R ^s1 is an alkyl group)). do. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 19, more preferably 2 to 11, even more preferably 2 to 7, unless otherwise specified. The alkoxycarbonyl group includes, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group and the like.

An alkenyloxycarbonyl group is a monovalent group in which an alkenyloxy group is bonded to one side of a carbonyl group (that is, a group represented by R ^s2 —O—C(═O)—(R ^s2 is an alkenyl group)). means The number of carbon atoms in the alkenyloxycarbonyl group is preferably 3-19, more preferably 3-11, even more preferably 3-7, unless otherwise specified. Examples of alkenyloxycarbonyl groups include vinyloxycarbonyl groups and propenyloxycarbonyl groups (allyloxycarbonyl groups, 1-propenyloxycarbonyl groups, isopropenyloxycarbonyl groups) and the like.

An aryloxycarbonyl group is a monovalent group in which an aryloxy group is bonded to one side of a carbonyl group (that is, a group represented by R ^s3 —O—C(=O)—(R ^s3 is an aryl group)). means The number of carbon atoms in the aryloxycarbonyl group is preferably 7-19, particularly preferably 7-11, unless otherwise specified. The aryloxycarbonyl group includes, for example, a phenoxycarbonyl group, a 1-naphthoxycarbonyl group, a 2-naphthoxycarbonyl group and the like.

An aralkyloxycarbonyl group is a monovalent group in which an aralkyloxy group is bonded to one side of a carbonyl group (that is, a group represented by R ^s4 —O—C(=O)—(R ^s4 is an aralkyl group)). means The number of carbon atoms in the aralkylcarbonyl group is preferably 7-19, particularly preferably 7-11, unless otherwise specified. The aralkyloxycarbonyl group includes, for example, a benzyloxycarbonyl group, an α-methylbenzyloxycarbonyl group and the like.

An alkylamino group means an amino group mono-substituted with an alkyl group (that is, a group represented by R ^s1 —NH— (R ^s1 is an alkyl group)). The number of carbon atoms in the alkylamino group is preferably 1-18, more preferably 1-10, and even more preferably 1-6, unless otherwise specified. The alkylamino group includes, for example, N-methylamino group, N-ethylamino group, N-propylamino group and the like. A di(alkyl)amino group means an amino group di-substituted with an alkyl group (that is, a group represented by (R ^s1 —) ₂ N—(R ^s1 is independently an alkyl group)). The number of carbon atoms in the di(alkyl)amino group is preferably 2 to 18, more preferably 2 to 10, even more preferably 2 to 6, unless otherwise specified. The di(alkyl)amino group includes, for example, N,N-dimethylamino group, N,N-diethylamino group, N-ethyl-N-methylamino group, N,N-dipropylamino group and the like.

An alkenylamino group means an amino group mono-substituted with an alkenyl group (that is, a group represented by R ^s2 —NH— (R ^s2 is an alkenyl group)). The number of carbon atoms in the alkenylamino group is preferably 2 to 19, more preferably 2 to 11, even more preferably 2 to 7, unless otherwise specified. Examples of alkenylamino groups include N-vinylamino groups and N-allylamino groups. The alkylalkenylamino group is an amino group substituted with both an alkyl group and an alkenyl group (that is, (R ^s1 -) (R ^s2 -) N- (R ^s1 is an alkyl group and R ^s2 is an alkenyl group). group). The number of carbon atoms in the alkylalkenylamino group is preferably 3 to 19, more preferably 3 to 11, even more preferably 3 to 7, unless otherwise specified. The alkylalkenylamino group includes, for example, N-methyl-N-vinylamino group, N-allyl-N-methylamino group and the like.

An alkylcarbonylamino group means an amino group monosubstituted with an alkylcarbonyl group (that is, a group represented by R ^s1 -C(=O)-NH- (R ^s1 is an alkyl group)). The number of carbon atoms in the alkylcarbonylamino group is preferably 2 to 19, more preferably 2 to 11, even more preferably 2 to 7, unless otherwise specified. The alkylcarbonylamino group includes, for example, N-acetylamino group, N-propanoylamino group, N-butanoylamino group and the like.

An alkenylcarbonylamino group means an amino group mono-substituted with an alkenylcarbonyl group (that is, a group represented by R ^s2 -C(=O)-NH- (R ^s2 is an alkenyl group)). The number of carbon atoms in the alkenylcarbonylamino group is preferably 3-20, more preferably 2-11, even more preferably 2-7, unless otherwise specified. Examples of alkenylcarbonylamino groups include N-vinylcarbonylamino group, N-allylcarbonylamino group, N-(1-propenylcarbonyl)amino group, N-isopropenylcarbonylamino group and the like.

An alkylcarbamoyl group means a carbamoyl group mono-substituted with an alkyl group (that is, a group represented by R ^s1 —NH—C(═O)—(R ^s1 is an alkyl group)). The number of carbon atoms in the alkylcarbamoyl group is preferably 2 to 19, more preferably 2 to 11, even more preferably 2 to 7, unless otherwise specified. The alkylcarbamoyl group includes, for example, N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group and the like.

An alkenylcarbamoyl group means a carbamoyl group mono-substituted with an alkenyl group (that is, a group represented by R ^s2 —NH—C(═O)—(R ^s2 is an alkenyl group)). The number of carbon atoms in the alkenylcarbamoyl group is preferably 3 to 20, more preferably 3 to 12, even more preferably 3 to 8, unless otherwise specified. Examples of alkenylcarbamoyl groups include N-vinylcarbamoyl groups and N-allylcarbamoyl groups.

A non-aromatic ring means a ring other than an aromatic ring having aromaticity throughout the ring. A non-aromatic ring is a non-aromatic carbocyclic ring having only carbon atoms as ring-constituting atoms, or a non-aromatic heterocyclic ring having heteroatoms such as oxygen, nitrogen and sulfur atoms in addition to carbon atoms as ring-constituting atoms. It can be a ring. The non-aromatic ring may be a monocyclic non-aromatic ring or a polycyclic non-aromatic ring, and a partially aromatic condensed ring obtained by partially condensing an aromatic ring may also be used. include. The non-aromatic ring may be a saturated ring consisting only of a single bond, or an unsaturated ring having a double bond in addition to the single bond. The non-aromatic ring is preferably a 3- to 21-membered non-aromatic ring, more preferably a 4- to 18-membered non-aromatic ring, and even more preferably a 5- to 14-membered non-aromatic ring.

Suitable specific examples of the "non-aromatic ring" in the "optionally substituted non-aromatic ring" formed by R ¹ and R ² include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, monocyclic nonane rings such as cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclopentene ring, cyclopentadiene ring, cyclohexene ring, 1,3-cyclohexadiene ring, and 1,4-cyclohexadiene ring; aromatic carbocyclic ring; 1,3-dioxane ring, 1,3-dioxolane ring, tetrahydropyran ring, tetrahydrofuran ring, 2,3-dihydro-2H-pyran ring, 4,5-dihydro-2H-pyran ring, 2H- Examples include monocyclic non-aromatic heterocycles such as pyran ring, 4H-pyran ring, 2,3-dihydrofuran ring, and 2,5-dihydrofuran ring.

When R ¹ and R ² form an "optionally substituted non-aromatic ring", formula (A):

[In the formula, each symbol is as described above. ]
In one embodiment, the partial structure represented by formulas (AA1) to (AA10):

[In the formula,
A ¹ and A ² each independently represent -CO- or -CR ^a R ^b -;
B ¹ and B ² each independently represent -O-, -NR ^c - or -CR ^a R ^b -;
C ¹ represents -O- or -NR ^c -;
R ^a and R ^b each independently represent a hydrogen atom or a substituent, and two R ^a bonded to adjacent carbon atoms are bonded together and optionally have a substituent An aromatic ring or an optionally substituted aromatic ring may be formed, and R ^a and R ^b bonded to the same carbon atom may be bonded together and may have a substituent. may form a good non-aromatic ring;
R ^c each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group . ]
It is preferably a structure represented by; more preferably a structure represented by formula (AA1) or (AA3); formulas (Aa1) to (Aa5):

[In the formula, each symbol is as described above. ]
The structure represented by is particularly preferred.

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

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

C ¹ denotes -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, and two R ^a bonded to adjacent carbon atoms are bonded together and optionally have a substituent An aromatic ring or an optionally substituted aromatic ring may be formed, and R ^a and R ^b bonded to the same carbon atom may be bonded together and may have a substituent. may form a good non-aromatic ring.

Preferred specific examples of the "non-aromatic ring" in the "optionally substituted non-aromatic ring" formed by R ^a and R ^b or two R ^a are, for example, a cyclobutane ring and a cyclopentane ring. , cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring and other monocyclic non-aromatic saturated carbocyclic rings; bicyclo[2.2.1]heptane ring (norbornane ring), bicyclo[4.4.0]decane ring (decane ring), bicyclo[5.3.0]decane ring, bicyclo[4.3.0]nonane ring (hydrindane 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 ]undecane ring and other bicyclic rings non-aromatic saturated carbocyclic ring having a system or higher; A non-aromatic carbocyclic ring in which an aromatic ring (benzene ring, naphthalene ring, etc.) is partially condensed, such as a dihydrophenanthrene ring.

The "substituent" represented by R ^a and R ^b and the "substituent" in the "optionally substituted aromatic ring" formed by two R ^a are not particularly limited, For example, 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 above).

The "substituent" in the "optionally substituted non-aromatic ring" formed by R ^a and R ^b or two R ^a is not particularly limited, but 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 , — monovalent substituents such as NHR ^x , —N(R ^x ) ₂ , —COOR ^x , —OCOR ^x , —CONH ₂ , —CONHR ^x , —CON(R ^x ) ₂ , —NHCOR ^x , ═O, or two valent substituents (R ^x is as described above).

An aromatic ring means a ring that follows Huckel's rule and has 4p+2 electrons (p is a natural number) in the π electron system on the ring. The aromatic ring is an aromatic carbocyclic ring having only carbon atoms as ring-constituting atoms, or an aromatic heterocyclic ring having a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom in addition to a carbon atom as a ring-constituting atom. obtain. The aromatic ring may be a monocyclic aromatic ring or a polycyclic aromatic ring. In one embodiment, the aromatic ring is preferably a 5- to 14-membered aromatic ring, more preferably a 6- to 14-membered aromatic ring, and even more preferably a 6- to 10-membered aromatic ring.

Examples of the "aromatic ring" in the "optionally substituted aromatic ring" formed by two R ^a include benzene ring, naphthalene ring, anthracene ring, and phenanthrene ring.

R ^a and R ^b are, in one embodiment, 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, an alkyl-substituted aryl group, an alkenyl substituted aryl group, alkoxy group, alkenyloxy group, aryloxy group, aralkyloxy group, alkylcarbonyl group, alkenylcarbonyl group, arylcarbonyl group, aralkylcarbonyl group, alkylcarbonyloxy group, alkenylcarbonyloxy group, arylcarbonyloxy group, an aralkylcarbonyloxy group, an alkyloxycarbonyl group, an alkenyloxycarbonyl group, an aryloxycarbonyl group, or an aralkyloxycarbonyl group; more preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or an alkyl-substituted aryl , an alkenyl-substituted aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, or an aralkyloxy group; more preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, or It is an alkenyl-substituted aryl group; particularly preferably a hydrogen atom or an alkyl group.

R ^c each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group .

The “substituent” in the “alkyl group optionally having substituents” represented by R ^c and the “substituent” in the “alkenyl group optionally having substituents” represented by R ^c are particularly limited For example, 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 ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , -NHCOR ^x (R ^x is as described above).

R ^y is a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, an aryl group, an alkyl-substituted aryl group, an alkenyl-substituted aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an alkylcarbonyl group; , alkenylcarbonyl group, arylcarbonyl group, aralkylcarbonyl group, alkylcarbonyloxy group, alkenylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group, alkyloxycarbonyl group, alkenyloxycarbonyl group, aryloxycarbonyl group, aralkyloxy substituted with a group selected from a carbonyl group, an alkylamino group, a di(alkyl)amino group, an alkenylamino group, an alkylalkenylamino group, an alkylcarbonylamino group, an alkenylcarbonylamino group, an alkylcarbamoyl group, and an alkenylcarbamoyl group; is a good aryl group.

The “substituent” in the “optionally substituted aryl group” represented by R ^c is not particularly limited, but 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 , Monovalent substituents such as —COOR ^x , —OCOR ^x , —CONH ₂ , —CONHR ^x , —CON(R ^x ) ₂ and —NHCOR ^x (R ^x is as described above).

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

When R ¹ and R ² do not form an “optionally substituted non-aromatic ring”, formula (A):

[In the formula, each symbol is as described above. ]
In one embodiment, the partial structure represented by formulas (Ab1) to (Ab10):

Each R independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.

The “substituent” in the “alkyl group optionally having substituents” represented by R and the “substituent” in the “alkenyl group optionally having substituents” represented by R are particularly limited for example, 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 ^x , —N(R ^x ) ₂ , —COOR ^x , —OCOR ^x , —CONH ₂ , —CONHR ^x , —CON(R ^x ) ₂ , —NHCOR ^x, etc. Monovalent substituents are included (R ^x and R ^y are as described above).

The "substituent" in the "optionally substituted aryl group" represented by R is not particularly limited, but 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 , — Monovalent substituents such as COOR ^x , —OCOR ^x , —CONH ₂ , —CONHR ^x , —CON(R ^x ) ₂ and —NHCOR ^x (R ^x is as described above).

In one embodiment, each R is independently preferably
(1) halogen atoms, -NO ₂ , -CN, -COH, -OH, -NH ₂ , -COOH, -R ^y , -COR ^x , -OR ^x , -NHR ^x , -N(R ^x ) ₂ , an alkyl group optionally substituted with a group selected from -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ and -NHCOR ^x ;
(2) 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 an alkenyl group optionally substituted with a group selected from; or (3) a 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 (R ^x and R ^y are as described above) optionally substituted with a group selected from —NHCOR ^x .

In one embodiment, each R is, more preferably, independently
(1) -R ^y , -COR ^x , -OR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , and -NHCOR an alkyl group optionally substituted with a group selected from ^x ;
(2) -R ^y , -COR ^x , -OR ^x , -N(R ^x ) ₂ , -COOR ^x , -OCOR ^x , -CONH ₂ , -CONHR ^x , -CON(R ^x ) ₂ , and -NHCOR an alkenyl group optionally substituted with a group selected from ^x ; or (3) -R ^x , -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 described above) optionally substituted with a group selected from —NHCOR ^x .

In one embodiment, R are each independently more preferably
(1) (a) an aryl group optionally substituted with a group selected from an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, an alkylcarbonyl group, an alkenylcarbonyl group, and a di(alkyl)amino group; ) alkoxy group, (c) alkenyloxy group, (d) alkylcarbonyl group, (e) alkenylcarbonyl group, (f) alkylcarbonyloxy group, (g) alkenylcarbonyloxy group, (h) alkyloxycarbonyl group, ( i) alkenyloxycarbonyl group, (j) di(alkyl)amino group, (k) alkylcarbonylamino group, (l) alkenylcarbonylamino group, (m) alkylcarbamoyl group, and (n) alkenylcarbamoyl group an alkyl group optionally substituted with a group;
(2) (a) an aryl group optionally substituted with a group selected from an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, an alkylcarbonyl group, an alkenylcarbonyl group, and a di(alkyl)amino group; ) alkoxy group, (c) alkenyloxy group, (d) alkylcarbonyl group, (e) alkenylcarbonyl group, (f) alkylcarbonyloxy group, (g) alkenylcarbonyloxy group, (h) alkyloxycarbonyl group, ( i) alkenyloxycarbonyl group, (j) di(alkyl)amino group, (k) alkylcarbonylamino group, (l) alkenylcarbonylamino group, (m) alkylcarbamoyl group, and (n) alkenylcarbamoyl group or (3) an aryl group optionally substituted by a group selected from (a) an alkyl group and an alkenyl group, (b) an alkyl group, (c) an alkenyl group, (d) alkoxy group, (e) alkenyloxy group, (f) alkylcarbonyl group, (g) alkenylcarbonyl group, (h) alkylcarbonyloxy group, (i) alkenylcarbonyloxy group, (j) alkyloxycarbonyl group , (k) an alkenyloxycarbonyl group, (l) a di(alkyl)amino group, (m) an alkylcarbonylamino group, (n) an alkenylcarbonylamino group, (o) an alkylcarbamoyl group, and (p) an alkenylcarbamoyl group It is an aryl group optionally substituted with a selected group.

In one embodiment, each R is independently particularly preferably
(1) (a) aryl group, (b) alkoxy group, (c) alkenyloxy group, (d) alkylcarbonyl group, (e) alkenylcarbonyl group, (f) alkylcarbonyloxy group, (g) alkenylcarbonyloxy an alkyl group optionally substituted with a group selected from a group, (h) an alkyloxycarbonyl group, and (i) an alkenyloxycarbonyl group;
(2) (a) aryl group, (b) alkoxy group, (c) alkenyloxy group, (d) alkylcarbonyl group, (e) alkenylcarbonyl group, (f) alkylcarbonyloxy group, (g) alkenylcarbonyloxy (h) an alkyloxycarbonyl group, and (i) an alkenyl group optionally substituted with a group selected from an alkenyloxycarbonyl group; or (3) (a) an aryl group, (b) an alkyl group, (c ) alkenyl group, (d) alkoxy group, (e) alkenyloxy group, (f) alkylcarbonyl group, (g) alkenylcarbonyl group, (h) alkylcarbonyloxy group, (i) alkenylcarbonyloxy group, (j) It is an aryl group optionally substituted with a group selected from an alkyloxycarbonyl group and (k) an alkenyloxycarbonyl group.

Formula (A):

[In the formula, each symbol is as described above. ]
Specific examples of the partial structure represented by are not particularly limited, but the formulas (A-1) to (A-437):

The structure represented by is mentioned.

R ³ and R ⁴ each independently represent a substituent.

The “substituent” represented by R ³ and R ⁴ is not particularly limited, but examples include 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 , —CONHR ^x , —CON(R ^x ) ₂ , —NHCOR ^x and the like (R ^x is as defined above).

R ³ and R ⁴ are, in one embodiment, each independently preferably an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkenyl-substituted aryl group, an alkoxy group, an alkenyloxy group, an aryl an oxy group or an aralkyloxy group; more preferably an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, or an alkenyl-substituted aryl group; more preferably an alkyl group; Preferred are alkyl groups of 4 or more carbon atoms; even more preferred are alkyl groups of 4 to 14 carbon atoms; and particularly preferred are tert-butyl groups.

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

"Aromatic carbocyclic ring" means a hydrocarbon ring that follows Hückel's rule and has 4p+2 electrons (p is a natural number) in the π electron system on the ring. Aromatic carbocycles have only carbon atoms as ring atoms. The aromatic carbocycle may be a monocyclic aromatic carbocycle or a polycyclic fused aromatic carbocycle. In one embodiment, the aromatic carbocyclic ring is preferably a 6- to 18-membered aromatic carbocyclic ring, more preferably a 6- to 14-membered aromatic carbocyclic ring, and even more preferably a 6- to 10-membered aromatic carbocyclic ring.

Examples of the "aromatic carbocyclic ring" in the "optionally substituted aromatic carbocyclic ring" representing ring X ¹ and ring X ² include benzene ring, naphthalene ring, anthracene ring, and phenanthrene ring. be done.

The “substituent” in the “optionally substituted aromatic carbocyclic ring” representing ring X ¹ and ring X ² is not particularly limited, but examples include 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 , — Monovalent substituents such as N(R ^x ) ₂ , —COOR ^x , —OCOR ^x , —CONH ₂ , —CONHR ^x , —CON(R ^x ) ₂ and —NHCOR ^x (R ^x is the above street).

In one embodiment, ring X ¹ and ring X ² are each independently preferably (1) an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkenyl-substituted aryl group, an alkoxy group, Benzene ring optionally substituted with a group selected from an alkenyloxy group, an aryloxy group, and an aralkyloxy group, or (2) an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkenyl-substituted aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, and an aralkyloxy group; more preferably an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl a benzene ring optionally substituted with a group selected from a substituted aryl group, an alkenyl-substituted aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, and an aralkyloxy group; more preferably an alkyl group, an alkenyl group, A benzene ring optionally substituted with a group selected from an aryl group, an aralkyl group, an alkyl-substituted aryl group, and an alkenyl-substituted aryl group; particularly preferably a benzene ring optionally substituted with an alkyl group.

Y represents a single bond or an organic group.

The organic group is not particularly limited, but in one embodiment, for example, one or more (eg, 1 to 100, preferably 1 to 100) selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. 50, particularly preferably 1 to 20) skeletal atoms, non-skeletal atoms are composed of hydrogen atoms or halogen atoms, and have a linear structure, a branched chain structure and / or a cyclic It may contain a structure and may be a group containing no aromatic ring or a group containing an aromatic ring. Examples of the organic group include -CR ^A R ^B -, -O-, -S-, -SO-, -SO ₂ -, -CONH-, -NHCO- and the like (provided that R ^A and R ^B each independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, R ^A and R ^B are bonded together, It may form a non-aromatic ring which may have a substituent.).

a indicates 0 or 1.

p and q each independently represent 0, 1, 2, 3, or 4; in one embodiment, preferably 0, 1, 2, or 3; more preferably 0, 1, or 2; more preferably 0 or 1; particularly preferably 0.

Formula (B):

[In the formula, each symbol is as described above. ]
In one embodiment, the substructure represented by the formula (Ba):

[In the formula,
Y ¹ represents a single bond, -CR ^A R ^B -, -O-, -S-, -SO-, -SO ₂ -, -CONH- or -NHCO-;
^RA and ^RB ^{each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, and RA and RB} ^together may be combined to form a non-aromatic ring optionally having a substituent;
R ⁵ and R ⁶ each independently represent a substituent;
r and s each independently represent 0, 1, 2, 3, or 4;
Others are as above. ]
It is preferably a structure represented by the formula (Bb):

[In the formula,
b represents 0 or 1;
Other symbols are as above. ]
The structure represented by is particularly preferred.

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

^RA and ^RB ^{each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, and RA and RB} ^together may combine together to form a non-aromatic ring which may have a substituent.

Preferred specific examples of the "non-aromatic ring" in the "optionally substituted non-aromatic ring" formed by R ^A and R ^B are R ^a and R ^b or two R ^a Preferred specific examples of the “non-aromatic ring” in the “optionally substituted non-aromatic ring” are the same as those mentioned above.

The “substituent” in the “alkyl group optionally having substituent(s)” represented by R ^A and R ^B is not particularly limited, but examples 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 ^x (R ^x and R ^y are as described above). ).

The “substituent” in the “optionally substituted aryl group” represented by R ^A and R ^B is not particularly limited, but examples include 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 , —CONHR ^x , —CON(R ^x ) ₂ , —NHCOR ^x (R ^x is as described above).

The “substituent” in the “optionally substituted non-aromatic ring” formed by R ^A and R ^B is not particularly limited, but 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 and other monovalent or divalent substituents. (R ^x as above).

In one embodiment, R ^A and R ^B are each independently preferably (1) a hydrogen atom, (2) a halogen atom, an aryl group, an alkyl-substituted aryl group, an alkenyl-substituted aryl group, an alkoxy group, an alkenyloxy an alkyl group optionally substituted by a group selected from groups, aryloxy groups, and aralkyloxy groups, or (3) halogen atoms, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, alkyl-substituted aryl groups, alkenyl-substituted represents an aryl group optionally substituted with a group selected from an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group and an aralkyloxy group, wherein R ^A and R ^B are bonded together, a halogen atom, may be substituted with a group selected from an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkenyl-substituted aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, and an oxo group; may form a good non-aromatic ring.

In one embodiment, R ^A and R ^B each independently more preferably represent (1) a hydrogen atom or (2) an alkyl group optionally substituted with a halogen atom, and R ^A and R ^B are bonded together and selected from (A) a monocyclic non-aromatic saturated carbocyclic ring optionally substituted by a group selected from an alkyl group and an aryl group, (B) an alkyl group and an aryl group A bicyclic or higher non-aromatic saturated carbocyclic ring optionally substituted by a group, or (C) an alkyl group, and an aryl group optionally substituted by a group selected from an aromatic ring (benzene ring or naphthalene ring) may form a condensed non-aromatic carbocyclic ring.

In one embodiment, R ^A and R ^B each independently represent, more preferably, a hydrogen atom or an alkyl group, and at least one of them is an alkyl group having 4 or more carbon atoms, or R ^A and R ^B are bonded together and may be substituted with a 5-membered or more (preferably 6-membered or more) monocyclic non-aromatic saturated carbocyclic ring optionally substituted with an alkyl group, or an alkyl group. It forms a 6- or more-membered bicyclic or higher non-aromatic saturated carbocyclic ring.

In one embodiment, R ^A and R ^B each independently represent, more preferably, a hydrogen atom or an alkyl group, and at least one is an alkyl group having 4 to 18 carbon atoms, or R ^A and R ^B are bonded together to form a 5- to 18-membered (preferably 6 to 18-membered) monocyclic non-aromatic saturated carbocyclic ring optionally substituted by an alkyl group having 1 to 6 carbon atoms; Form.

R ^A and R ^B are, in one embodiment, particularly preferably R ^A and R ^B joined together to form a cyclododecane ring.

^R5 and ^R6 each independently represent a substituent.

The “substituent” represented by R ⁵ and R ⁶ is not particularly limited, but examples include 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 , —CONHR ^x , —CON(R ^x ) ₂ , —NHCOR ^x and the like (R ^x is as defined above).

R ⁵ and R ⁶ are, in one embodiment, each independently preferably an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkenyl-substituted aryl group, an alkoxy group, an alkenyloxy group, an aryl an oxy group or an aralkyloxy group; more preferably an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, or an alkenyl-substituted aryl group; more preferably an alkyl group; Preferred are alkyl groups of 4 or more carbon atoms; even more preferred are alkyl groups of 4 to 18 carbon atoms; and particularly preferred are tert-butyl groups.

In one embodiment of R ⁵ and R ⁶ , preferably at least one of R ⁵ and R ⁶ is an alkyl group having 4 or more carbon atoms; more preferably at least one of R ⁵ and R ⁶ is an alkyl group having 4 to 18 carbon atoms; particularly preferably at least one of R ⁵ and R ⁶ is a tert-butyl group.

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

b represents 0 or 1; in one embodiment, it is preferably 1. Thus, either a represents 0, or a represents 1 and b represents 0 or 1; be.

Formula (B):

[In the formula, each symbol is as described above. ]
Specific examples of the partial structure represented by are not particularly limited, but the formulas (B-1) to (B-41):

[In the formula, each symbol is as described above. ]
The structure represented by is mentioned.

In one embodiment when the partial structure represented by formula (B) is a structure represented by formula (Bb), preferably
R ¹ and R ² are each independently a hydrogen atom, —CN, —NO ₂ , —COH, —R, —COR, or —COOR, and R ¹ and R ² are bonded together; may form a non-aromatic ring which may have a substituent;
Each R is independently substituted with a group selected from (1) (a) an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, an alkylcarbonyl group, an alkenylcarbonyl group, and a di(alkyl)amino group. aryl group, (b) alkoxy group, (c) alkenyloxy group, (d) alkylcarbonyl group, (e) alkenylcarbonyl group, (f) alkylcarbonyloxy group, (g) alkenylcarbonyloxy group, ( h) an alkyloxycarbonyl group, (i) an alkenyloxycarbonyl group, (j) a di(alkyl)amino group, (k) an alkylcarbonylamino group, (l) an alkenylcarbonylamino group, (m) an alkylcarbamoyl group, and ( n) an alkyl group optionally substituted with a group selected from alkenylcarbamoyl groups; (2) (a) alkyl groups, alkenyl groups, alkoxy groups, alkenyloxy groups, alkylcarbonyl groups, alkenylcarbonyl groups, and di(alkyl ) an aryl group optionally substituted by a group selected from an amino group, (b) an alkoxy group, (c) an alkenyloxy group, (d) an alkylcarbonyl group, (e) an alkenylcarbonyl group, (f) an alkylcarbonyloxy (g) alkenylcarbonyloxy group, (h) alkyloxycarbonyl group, (i) alkenyloxycarbonyl group, (j) di(alkyl)amino group, (k) alkylcarbonylamino group, (l) alkenylcarbonylamino (m) an alkylcarbamoyl group, and (n) an alkenyl group optionally substituted with a group selected from an alkenylcarbamoyl group; or (3) (a) a group selected from an alkyl group and an alkenyl group. aryl group, (b) alkyl group, (c) alkenyl group, (d) alkoxy group, (e) alkenyloxy group, (f) alkylcarbonyl group, (g) alkenylcarbonyl group, (h) alkyl carbonyloxy group, (i) alkenylcarbonyloxy group, (j) alkyloxycarbonyl group, (k) alkenyloxycarbonyl group, (l) di(alkyl)amino group, (m) alkylcarbonylamino group, (n) alkenyl an aryl group optionally substituted with a group selected from a carbonylamino group, (o) an alkylcarbamoyl group, and (p) an alkenylcarbamoyl group;
R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group, alkenyl group, aryl group, aralkyl group, alkyl-substituted aryl group, alkenyl-substituted aryl group, alkoxy group, alkenyloxy group, aryloxy group , or an aralkyloxy group;
R ^A and R ^B each independently represent (1) a hydrogen atom, (2) a halogen atom, an aryl group, an alkyl-substituted aryl group, an alkenyl-substituted aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, and an aralkyl an alkyl group optionally substituted with a group selected from an oxy group, or (3) a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, an alkenyl-substituted aryl group, an alkoxy group, an alkenyloxy represents an aryl group optionally substituted with a group selected from groups, aryloxy groups, and aralkyloxy groups, wherein R ^A and R ^B are bonded together to form a halogen atom, an alkyl group, an alkenyl group, an aryl group; , an aralkyl group, an alkyl-substituted aryl group, an alkenyl-substituted aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, and an oxo group. may;
a and b each independently represent 0 or 1;
p, q, r and s each independently represent 0, 1, 2, 3 or 4;

In one embodiment when the partial structure represented by formula (B) is a structure represented by formula (Bb), more preferably,
R ¹ and R ² are each independently a hydrogen atom, —R, —COR, or —COOR, and R ¹ and R ² are bonded together and optionally have a substituent may form an aromatic ring;
R is each independently (1) (a) aryl group, (b) alkoxy group, (c) alkenyloxy group, (d) alkylcarbonyl group, (e) alkenylcarbonyl group, (f) alkylcarbonyloxy group, (g) an alkenylcarbonyloxy group, (h) an alkyloxycarbonyl group, and (i) an alkyl group optionally substituted by a group selected from an alkenyloxycarbonyl group; (2) (a) an aryl group, ( b) alkoxy group, (c) alkenyloxy group, (d) alkylcarbonyl group, (e) alkenylcarbonyl group, (f) alkylcarbonyloxy group, (g) alkenylcarbonyloxy group, (h) alkyloxycarbonyl group, and (i) an alkenyl group optionally substituted with a group selected from an alkenyloxycarbonyl group; or (3) (a) an aryl group, (b) an alkyl group, (c) an alkenyl group, (d) an alkoxy group, (e) alkenyloxy group, (f) alkylcarbonyl group, (g) alkenylcarbonyl group, (h) alkylcarbonyloxy group, (i) alkenylcarbonyloxy group, (j) alkyloxycarbonyl group, and (k) alkenyl an aryl group optionally substituted with a group selected from an oxycarbonyl group;
R3 ^, ^R4 , ^R5 and ^R6 are each independently an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkyl-substituted aryl group, or an alkenyl-substituted aryl group;
In one embodiment, R ^A and R ^B each independently more preferably represent (1) a hydrogen atom or (2) an alkyl group optionally substituted with a halogen atom, and R ^A and R ^B are bonded together and selected from (A) a monocyclic non-aromatic saturated carbocyclic ring optionally substituted by a group selected from an alkyl group and an aryl group, (B) an alkyl group and an aryl group A bicyclic or higher non-aromatic saturated carbocyclic ring optionally substituted by a group, or (C) an alkyl group, and an aryl group optionally substituted by a group selected from an aromatic ring (benzene ring or naphthalene ring) may form a condensed non-aromatic carbocyclic ring;
a and b each independently represent 0 or 1;
p, q, r and s each independently represent 0, 1, 2, 3 or 4;

In one embodiment when the partial structure represented by formula (B) is a structure represented by formula (Bb), preferably
If a is 0,
s is 1 or more, and at least one of R ⁶ is an alkyl group having 4 or more carbon atoms;
If a is 1 and b is 0,
the sum of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is an alkyl group having 4 or more carbon atoms;
If a is 1 and b is 1,
(1) the sum of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is an alkyl group having 4 or more carbon atoms, and/or (2-1) R ^A and R ^B are represents a hydrogen atom or an alkyl group, and at least one of which is an alkyl group having 4 or more carbon atoms, or (2-2) R ^A and R ^B are bonded together and substituted with an alkyl group 5-membered or more (preferably 6-membered or more) monocyclic non-aromatic saturated carbocyclic ring, or 6-membered or more bicyclic or higher non-aromatic saturated carbocyclic ring optionally substituted with an alkyl group Form.

In one embodiment when the partial structure represented by formula (B) is a structure represented by formula (Bb), more preferably,
If a is 0,
s is 1 or more, and at least one of R ⁶ is an alkyl group having 4 to 18 carbon atoms;
If a is 1 and b is 0,
the sum of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is an alkyl group having 4 to 18 carbon atoms;
If a is 1 and b is 1,
(1) the sum of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is an alkyl group having 4 or more carbon atoms, and/or (2-1) R ^A and R ^B are represents a hydrogen atom or an alkyl group, and at least one is an alkyl group having 4 to 18 carbon atoms, or (2-2) R ^A and R ^B are bonded together and have 1 to 6 carbon atoms It forms a 5- to 18-membered (preferably 6- to 18-membered) monocyclic non-aromatic saturated carbocyclic ring which may be substituted with an alkyl group.

In one embodiment when the partial structure represented by formula (B) is a structure represented by formula (Bb), particularly preferably,
If a is 0,
s is 1 or more, and at least one of R ⁶ is a tert-butyl group;
If a is 1 and b is 0,
the sum of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is a tert-butyl group;
If a is 1 and b is 1,
(1) the sum of r and s is 1 or more, and at least one of R ⁵ and R ⁶ is a tert-butyl group, and/or (2) R ^A and R ^B together combine to form a cyclododecane ring.

In one embodiment of the polyether resin of the present invention, more preferably, the partial structure represented by formula (B) in formula (1) is a structure represented by formula (Ba), formula (2):

[In the formula, each symbol is as described above. ]
It has a repeating unit represented by The preferred range and specific examples of each structure in formula (2) are as described above.

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

[In the formula, each symbol is as described above. ]
It has a repeating unit represented by The preferred range and specific examples of each structure in formula (3) are as described above.

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

[In the formula, each symbol is as described above. ]
It has a repeating unit represented by any of Preferred ranges and specific examples of each structure in formulas (4-1) to (4-30) are as described above. Represented by formula (1) (more preferably formula (2), particularly preferably formula (3), most preferably formulas (4-1) to (4-30)) in the polyether resin molecule of the present invention The mass ratio of the repeating unit is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and particularly preferably 20% by mass or more.

Although 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, and still more preferably 20,000. 30,000 or more, 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, and still more preferably 300,000 or less. , particularly preferably 200,000 or less. The weight average molecular weight of the polyether resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

The dielectric loss tangent (Df) of the polyether resin of the present invention is not particularly limited, but when measured at 5.8 GHz and 23° C., in one embodiment, it is preferably 0.012 or less, more preferably 0. 0.010 or less, more preferably 0.009 or less, even more preferably 0.008 or less, even more preferably 0.007 or less, and particularly preferably 0.006 or less. The dielectric loss tangent (Df) of the polyether resin can be measured as in Test Example A2 below.

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

The polyether resin of the present invention may, in one embodiment, tend to be readily soluble in organic solvents that may even be used as developers in the manufacture of semiconductor package substrates. Organic solvents used as developers include, for example, acetone, ethyl acetate, ethyl alcohol, isopropyl alcohol, butyl alcohol, methoxyethanol, ethoxyethanol, propoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono butyl ether, cyclopentanone, cyclohexanone and the like. The solubility in these organic solvents is not particularly limited, but can be, for example, 30% by mass or more at 100°C.

The polyether resin of the present invention having a repeating unit represented by formula (1) has, for example, Ph ₃ P= CR ¹ R ² [However, each symbol is as described above. ] or (R ^h O) ₂ (O=)P-CHR ¹ R ² [wherein R ^h is an alkyl group and other symbols are as described above. ] under basic conditions (Wittig reaction or Horner-Wadsworth-Emmons reaction).

Further, in the polyether resin of the present invention having a repeating unit represented by formula (1), both R ¹ and R ² in formula (1) are -COR or -COOR, or When forming a ring, CH ₂ R ¹ R ² [wherein each symbol is as described above, for PEEK having a repeating unit represented by the following formula (1′). ] under basic conditions (Knoevenagel condensation reaction).

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

[In the formula, each symbol is as described above. ]
As the above reaction conditions, the general reaction conditions of the Wittig reaction, the Horner-Wadsworth-Emmons reaction, or the Knoevenagel condensation reaction can be used as they are or reaction conditions based thereon can be used. Examples of bases that can be used include piperazine and potassium carbonate. Moreover, you may use a solvent for reaction. Examples of solvents that can be used include N-methylpyrrolidone, tetrahydrofuran, and dimethyl ether. The reaction temperature can be appropriately set within the range of -80°C to 250°C. The reaction time can range from 0.1 hour to 50 hours. Further, after the reaction, it may be purified by a known method.

In addition, the above reaction rate for the structural unit represented by formula (1′) may be less than 100 mol %, whereby the polyether resin of the present invention contains A repeating unit may remain. In one embodiment, the reaction rate of the structural unit represented by formula (1′) is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and particularly preferably 40 mol%. It can be more than Therefore, in one embodiment, the residual rate of the repeating unit represented by formula (1′) in the polyether resin of the present invention is preferably less than 90 mol%, more preferably less than 80 mol%, and even more preferably less than 70 mol%. , particularly preferably less than 60 mol %.

PEEK having a repeating unit represented by the following formula (1′) is represented by a difluoro compound or a dichloro compound represented by the following formula (1″-a), and the following formula (1″-b). A dihydroxy compound can be produced by a polymerization reaction under basic conditions.

[In the formula, Hal each independently represents a fluorine atom or a chlorine atom, and other symbols are as described above. ]
As the above reaction conditions, general reaction conditions for polymerization reactions can be used as they are or reaction conditions based thereon can be used. As the base, for example, potassium carbonate or the like can be used. Moreover, you may use a solvent for reaction. As a solvent, for example, N-methylpyrrolidone or the like can be used. The reaction temperature can be appropriately set within the range of 100°C to 300°C. The reaction time can range from 0.1 hour to 50 hours. Further, after the reaction, it may be purified by a known method.

In addition, in the production method described above, further known reactions such as decarboxylation, deprotection, oxidation, reduction, radical cyclization, nucleophilic substitution, alkylation, halogenation, condensation, etc. Reactions may be combined.

<Resin composition>
The resin composition of the present invention contains a curable cross-linking agent in addition to the polyether resin of the present invention. The curable cross-linking agent may be, for example, a compound having two or more polymerizable groups such as epoxy group, vinylphenyl group, isopropenylphenyl group, allyl group, acryloyl group and methacryloyl group. A curable crosslinker can be a component that cures by self-polymerizing or cures by cross-linking the curing agent. Such resin compositions may be cured by heating or light irradiation. Such resin compositions may have superior 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. , more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, even more preferably 15 to 90% by mass, even more preferably 30 to 95% by mass, particularly preferably 50 to 90% by mass.

The curable cross-linking agent is preferably a photocurable cross-linking agent. Therefore, in a preferred embodiment, the resin composition of the present invention contains a photocurable cross-linking agent and a photopolymerization initiator in addition to the polyether resin of the present invention. Such a resin composition can have better resolution.

The photocurable cross-linking agent can be, for example, a compound having two or more radically polymerizable groups such as vinylphenyl, isopropenylphenyl, allyl, acryloyl, and methacryloyl groups. Examples of photocurable crosslinking agents include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecanedimethanol 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 acrylates, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dioxane glycol di(meth)acrylate (Meth)acrylates, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate , polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, tris ( 3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, polyhydric (meth)acrylate compounds such as ethoxylated isocyanuric acid tri(meth)acrylate, and the like. . The photocurable cross-linking agents may be used singly or in combination of two or more.

The content of the photocurable cross-linking agent for the polyether resin of the present invention in the resin composition of the present invention is not particularly limited, but is preferably 3 to 3 parts per 100 parts by mass of the polyether resin of the present invention. 25 parts by mass, more preferably 5 to 20 parts by mass, and even 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. More preferably 3 to 15 mass %, still more preferably 5 to 10 mass %.

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

Examples of oxime ester photopolymerization initiators include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (OXE01), [1-[9-ethyl-6-( 2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate (OXE02) and the like.

Phosphine oxide-based photopolymerization initiators include, for example, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, polyoxyethylene glycerin ether tris[phenyl( 2,4,6-trimethylbenzoyl)phosphinate] (Polymeric TPO-L) and the like.

Examples of α-hydroxyketone-based photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)phenyl]-2 -hydroxy-2-methylpropanone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one and the like.

Benzoin-based photopolymerization initiators include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Benzyl ketal photopolymerization initiators include, for example, 2,2-dimethoxy-2-phenylacetophenone.

Examples of α-aminoketone-based photopolymerization initiators include 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- 1-one, 2-methyl-1-(4-hexylphenyl)-2-morpholinopropan-1-one, 2-ethyl-2-(dimethylamino)-1-(4-morpholinophenyl)butane-1- one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(dimethylamino)-2-(4-methylphenylmethyl)-1-(4- morpholinophenyl)butan-1-one and the like. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the photopolymerization initiator for the polyether resin of the present invention in the resin composition of the present invention is not particularly limited, but is preferably 0.00 per 100 parts by mass of the polyether resin of the present invention. 1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, still 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, but when the non-volatile component of the resin composition is 100% by mass, it is preferably 0.1 to 10% by mass. , more preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass.

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

As a photosensitizer, for example, formula (5):

[wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an optionally substituted alkyl group, or a substituent; Indicates an alkoxy group which may be present. ]
It is preferable to contain a photosensitizer represented by.

As the “substituent” in the “optionally substituted alkyl group” and “optionally substituted alkoxy group” represented by R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ , but are not limited to, 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 ^x , —N(R ^x ) ₂ , —COOR ^x , —OCOR ^x , —CONH ₂ , —CONHR ^x , —CON(R ^x ) ₂ , Monovalent substituents such as —NHCOR ^x (R ^x and R ^y are as described above).

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

Although the content of the photosensitizer for the polyether resin of the present invention in the resin composition of the present invention is not particularly limited, it is preferably 0.1 per 100 parts by mass of the polyether resin of the present invention. to 20 parts by mass, more preferably 0.5 to 17 parts by mass, and even 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. is 3 to 15% by mass, more preferably 5 to 10% by mass.

The resin composition of the present invention may further contain other additives. Other additives include, for example, thermosetting resins such as epoxy resins and epoxy resin curing agents; curing accelerators; inorganic fillers such as silica; Surfactants such as cationic surfactants, anionic surfactants, silicone surfactants; thermoplastic resins; phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene Colorants such as black; polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol; thickeners such as bentone and montmorillonite; antifoaming agents such as silicone, fluorine, and vinyl resin; Fire retardants such as resins, antimony compounds, phosphorus compounds, aromatic condensed phosphates, and halogen-containing condensed phosphates are included. Other additives may be used singly or in combination of two or more. The content of each component can be appropriately set by those skilled in the art.

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, and dioxane; glycol ether solvents such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and propylene glycol monomethyl ether. ; glycol ether ester solvents such as propylene glycol monomethyl ether acetate; ketone solvents such as cyclohexanone, cyclopentanone, acetone, methyl ethyl ketone, methyl isobutyl ketone; pentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, and decalin Aliphatic hydrocarbon solvents; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and tetralin; methyl acetate, ethyl acetate, ethyl lactate, butyl lactate, γ-butyrolactone, methyl benzoate, α-acetyl-γ - ester solvents such as butyrolactone; chlorine solvents such as chloroform, methylene chloride and 1,2-dichloroethane; nitrile solvents such as acetonitrile; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2 - amide solvents such as pyrrolidone; sulfoxide solvents such as dimethylsulfoxide; An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of the organic solvent in the varnish-like resin composition before drying is not particularly limited, but is preferably 100 to 5000 parts by mass with respect to 100 parts by mass of the polyether resin of the present invention, More preferably 300 to 3000 parts by mass, still more preferably 500 to 1500 parts by mass.

The resin composition of the present invention is prepared by appropriately mixing each component, and if necessary, kneading means such as a three-roll mill, ball mill, bead mill and sand mill, or stirring means such as a super mixer, a planetary mixer and a high-speed rotating mixer. It can be produced by kneading or stirring with

The resin composition of the present invention can have excellent resolution. Therefore, in one embodiment, the resin composition of the present invention can be characterized in that the minimum opening diameter (minimum via diameter) of a via hole that can be formed by exposure and development is smaller. Therefore, in one embodiment, the minimum opening diameter when tested as in Test Example B1 below is preferably 25 μm or less, more preferably 20 μm or less, even more preferably 18 μm or less, even more preferably 15 μm or less, and even more preferably 15 μm or less. It may preferably be 12 μm or less, particularly preferably 10 μm or less.

The dielectric loss tangent (Df) of the cured product of the resin composition of the present invention is not particularly limited, but when measured at 5.8 GHz and 23 ° C., in one embodiment, preferably 0.018 or less, 0 .016 or less, 0.014 or less, 0.012 or less, more preferably 0.010 or less, even more preferably 0.009 or less, even more preferably 0.008 or less, even more preferably 0.007 or less, especially It is preferably 0.006 or less. The dielectric loss tangent (Df) of the cured product of the resin composition can be measured as in Test Example B2 below.

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

Applications of the resin composition of the present invention are not particularly limited, but include resin films, insulating resin sheets such as prepreg, insulating materials, silicon wafers, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, and buffers. It can be used in a wide range of applications such as coating films, underfill materials, die bonding materials, semiconductor sealing materials, hole-filling resins, and parts-embedding resins. Among them, a resin composition for an insulating layer of a printed wiring board (a printed wiring board having a cured product of the resin composition as an insulating layer), a resin composition for an interlayer insulating layer (a cured product of a resin composition used as an interlayer insulating layer printed wiring board), a resin composition for plating (printed wiring board in which plating is formed on a cured product of the resin composition), and a resin composition for solder resist (a cured product of the resin composition is soldered printed wiring board as resist), resin composition for rewiring formation layer of wafer level package (wafer level package with rewiring formation layer of cured resin composition), rewiring formation layer of fan-out wafer level package (Fan-out wafer level package with the cured product of the resin composition as the rewiring formation layer), the resin composition for the rewiring formation layer of the fan-out panel level package (The cured product of the resin composition is recycled Fan-out panel level package with wiring forming layer), resin composition for buffer coat (semiconductor device with cured product of resin composition as buffer coat), resin composition for insulating layer for display (cured resin composition It can be suitably used as a display using a material as an insulating layer.

Further, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition is used as an insulating layer for forming a rewiring layer to form a rewiring formation layer. (a resin composition for forming a rewiring layer) and a resin composition for sealing a semiconductor chip (a resin composition for sealing a semiconductor chip). A rewiring layer may be further formed on the encapsulation layer when the semiconductor chip package is manufactured.
(1) a step of laminating a temporary fixing film on a substrate;
(2) temporarily fixing the semiconductor chip on the temporary fixing film;
(3) forming a sealing layer on the semiconductor chip;
(4) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;
(5) Forming a rewiring layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been removed; and (6) Forming a rewiring layer as a conductor layer on the rewiring layer. forming process

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

<Insulating material>
The insulating material of the present invention comprises the polyether resin of the present invention.

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

Examples of the support include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), and polycarbonates (hereinafter sometimes abbreviated as "PC"). may be abbreviated.), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and polyethylene terephthalate film is particularly preferred.

A metal foil may also be used as the support. Examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

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

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

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. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

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

The resin composition layer may be protected with a protective film. By protecting the resin composition layer with the protective film, it is possible to suppress adhesion of dust and scratches on the surface of the resin composition layer. As the protective film, for example, a film made of the same material as the support can be used. Although the thickness of the protective film is not particularly limited, it is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, even more preferably in the range of 10 μm to 30 μm. The protective film preferably has a smaller adhesive force between the resin composition layer and the protective film than the adhesive force between the resin composition layer and the support.

A resin film can be produced, for example, by applying a resin composition onto a support using a die coater or the like and drying it as necessary to form a resin composition layer.

Drying may be carried out by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, but the resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition, for example, when using a resin composition containing 30% by mass to 60% by mass of the organic solvent, drying at 50 ° C. to 150 ° C. for 3 to 10 minutes A resin composition layer can be formed.

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

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

The semiconductor package substrate of the first embodiment of the present invention can be produced using the resin composition that is the first embodiment of the resin composition of the present invention, and the cured product of the resin composition is used as an insulating layer. . Specifically, the method for manufacturing a semiconductor package substrate includes:
(I) forming a resin composition layer formed of the resin composition of the present invention on a circuit board;
(II) a step of irradiating the resin composition layer with an actinic ray, and (III) a step of developing the resin composition layer,
in that order.

<Step (I)>
Methods of forming the resin composition layer include a method of directly applying a varnish-like resin composition onto a circuit board, and a method of using a resin film.

When the varnish-like resin composition is directly applied onto the circuit board, the resin composition layer is formed on the circuit board by drying and volatilizing the organic solvent.

Examples of coating methods for the resin composition include gravure coating, micro gravure coating, reverse coating, kiss reverse coating, die coating, slot die, lip coating, comma coating, blade coating, and roll coating. Method, knife coating method, curtain coating method, chamber gravure coating method, slot orifice method, spin coating method, slit coating method, spray coating method, dip coating method, hot melt coating method, bar coating method, applicator method, air knife coating method , a curtain flow coating method, an offset printing method, a brush coating method, a full-surface printing method using a screen printing method, and the like.

The resin composition may be applied in several times, may be applied in one time, or may be applied by combining a plurality of different methods. Among them, the die coating method is preferable because of its excellent uniform coatability. Also, in order to avoid contamination by foreign substances, it is preferable to perform the coating process in an environment such as a clean room where foreign substances are less likely to occur.

After applying the resin composition, dry it in a hot air oven or far infrared oven as necessary. The drying conditions are preferably 80° C. to 120° C. for 3 minutes to 13 minutes. Thus, a resin composition layer is formed on the circuit board.

Examples of circuit boards include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Here, the term "circuit board" refers to a board having a patterned conductor layer (circuit) formed on one or both sides of the support board as described above. In addition, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, a substrate in which one or both sides of the outermost layer of the multilayer printed wiring board is a patterned conductor layer (circuit) is also included here. included in the circuit board. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching, or the like.

On the other hand, when using a resin film, the resin composition layer side is laminated on one side or both sides of the circuit board using a vacuum laminator. In the lamination step, when the resin film has a protective film, after removing the protective film, the resin film and the circuit board are preheated as necessary, and the circuit is formed while pressing and heating the resin composition layer. Press onto the board. For the resin film, a method of laminating it on a circuit board under reduced pressure by a vacuum lamination method is preferably used.

Although the conditions for lamination are not particularly limited, for example, the crimping temperature (laminating temperature) is preferably 70° C. to 140° C., and the crimping pressure is preferably 1 kgf/cm ² to 11 kgf/cm ² (9.8 ×10 ⁴ N/m ² to 107.9×10 ⁴ N/m ² ), the pressure bonding time is preferably 5 seconds to 300 seconds, and the air pressure is 20 mmHg (26.7 hPa) or less. preferable. Moreover, the lamination process may be of a batch type or a continuous type using rolls. A vacuum lamination method can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. be able to.

<Step (II)>
After the resin composition layer is provided on the circuit board, an exposure step is performed in which a predetermined portion of the resin composition layer is irradiated with actinic rays through a mask pattern. Actinic rays include, for example, ultraviolet rays, visible rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. The irradiation dose of ultraviolet rays is approximately 10 mJ/cm ² to 1000 mJ/cm ² . The exposure method includes a contact exposure method in which a mask pattern is brought into close contact with a circuit board and a non-contact exposure method in which a parallel light beam is used for exposure without close contact.

In step (II), vias can be formed using, for example, a via pattern such as a round hole pattern as the mask pattern. The via diameter (opening diameter) is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. Although the lower limit is not particularly limited, it can be 0.1 μm or more, 0.5 μm or more, or the like.

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

In the case of the wet development, safe and stable developing solutions with good operability, such as alkaline solutions, aqueous developing solutions, and organic solvents, are used. As a developing method, known methods such as spraying, rocking immersion, brushing, scraping, and the like are appropriately adopted.

Examples of the alkaline aqueous solution 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; and sodium phosphate. , alkali metal phosphates such as potassium phosphate, aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and aqueous solutions of organic bases containing no metal ions such as tetraalkylammonium hydroxide, An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable because it does not contain metal ions and does not affect the semiconductor chip.

These alkaline aqueous solutions can contain surfactants, antifoaming agents, etc. in order to improve the development effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8-12, more preferably in the range of 9-11. Further, the base concentration of the alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected according to the developability of the resin composition layer, but is preferably 20°C to 50°C.

Organic solvents used as developers include, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. They are monobutyl ether, cyclopentanone and cyclohexanone.

The concentration of such an organic solvent is preferably 2% by mass to 90% by mass with respect to the total amount of the developer. Moreover, the temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such organic solvents can be used alone or in combination of two or more. Organic solvent-based developers used alone include, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

In pattern formation, if necessary, two or more developing methods may be used in combination. Development methods include a dip method, a battle method, a spray method, a high-pressure spray method, brushing, slapping, etc. The high-pressure spray method is suitable for improving resolution. When the spray method is employed, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

<Thermal curing (post-baking) process>
After completion of the step (III), a heat curing (post-baking) step is performed as necessary. Although curing of the resin composition layer may progress in the above-described steps (I) to (III), it is possible to further progress the curing of the resin composition in the thermosetting step to obtain an insulating layer having excellent mechanical strength. can be done. The post-baking process includes a heating process using a clean oven. The atmosphere during thermosetting may be in the air or in an inert gas atmosphere such as nitrogen. The heating conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but are preferably 150° C. to 250° C. for 20 minutes to 180 minutes, more preferably 160° C. ~230°C for 30 minutes to 120 minutes.

<Other processes>
The method for manufacturing a semiconductor package substrate may further include a drilling step and a desmear step after forming an insulating layer as a cured resin composition layer. These steps may be performed according to various methods known to those skilled in the art for use in the manufacture of semiconductor package substrates.

After forming the insulating layer, if desired, the insulating layer formed on the circuit board is subjected to a drilling process to form via holes and through holes. The drilling step can be carried out by a known method such as drilling, laser, plasma, or a combination of these methods if necessary, but a drilling step using a laser such as a carbon dioxide gas laser or a YAG laser is preferred.

The desmear process is a desmear process. Resin residue (smear) generally adheres to the inside of the opening formed in the drilling process. Since such smears cause electrical connection failures, processing for removing smears (desmear processing) is performed in this step.

Desmearing may be performed by dry desmearing, wet desmearing, or a combination thereof.

Examples of dry desmear treatment include desmear treatment using plasma. Desmearing using plasma can be performed using a commercially available plasma desmearing device. Among commercially available plasma desmear processing apparatuses, suitable examples for use in manufacturing semiconductor package substrates include a microwave plasma apparatus manufactured by Nissin Co., Ltd., and an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd., and the like.

Wet desmear treatment includes, for example, desmear treatment using an oxidizing agent solution. When the desmear treatment is performed using the oxidant solution, it is preferable to perform the swelling treatment with the swelling liquid, the oxidation treatment with the oxidant solution, and the neutralization treatment with the neutralization solution in this order. Examples of the swelling liquid include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment is preferably carried out by immersing the substrate having via holes and the like formed therein in a swelling liquid heated to 60° C. to 80° C. for 5 to 10 minutes. As the oxidizing agent solution, an aqueous alkaline permanganate solution is preferable. For example, a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. The oxidation treatment with the oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in the oxidizing agent solution heated to 60° C. to 80° C. for 10 minutes to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is preferably carried out by immersing the substrate after the oxidation treatment in the neutralizing solution at 30° C. to 50° C. for 3 to 10 minutes. As the neutralizing liquid, an acidic aqueous solution is preferable, and commercially available products include, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan.

When performing dry desmear treatment and wet desmear treatment in combination, dry desmear treatment may be performed first, or wet desmear treatment may be performed first.

Regardless of whether the insulating layer is formed as a rewiring forming layer, an interlayer insulating layer, or a solder resist, a drilling step and a desmear step may be performed after the thermosetting step. Moreover, in the method for manufacturing a semiconductor package substrate, a plating step may be further performed.

The plating process is a process of forming a conductor layer on an insulating layer. The conductor layer may be formed by sputtering after forming the insulating layer, or may be formed by combining electroless plating and electrolytic plating, or forming a plating resist having a pattern opposite to that of the conductor layer, The conductor layer may be formed only by electroless plating. As a method for subsequent pattern formation, for example, a subtractive method, a semi-additive method, or the like known to those skilled in the art can be used.

A semiconductor package substrate according to the second embodiment of the present invention can be manufactured using the resin composition described above, and a cured product of the resin composition is used as a rewiring formation layer. Specifically, the method for manufacturing a semiconductor package substrate includes:
(A) a step of laminating a temporary fixing film on a substrate;
(B) temporarily fixing the semiconductor chip on the temporary fixing film;
(C) forming a sealing layer on the semiconductor chip;
(D) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;
(E) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed;
(F) forming a rewiring layer as a conductor layer on the rewiring forming layer;
(G) forming a solder resist layer on the rewiring layer;
including. Further, the method for manufacturing the semiconductor chip package includes:
(H) a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and singulating them;
may contain

<Step (A)>
Step (A) is a step of laminating a temporary fixing film on a substrate. The conditions for laminating the substrate and the temporary fixing film are not particularly limited, but for example, the pressure bonding temperature (laminating temperature) is preferably 70° C. to 140° C., and the pressure bonding pressure is preferably 1 kgf/cm ² to 11 kgf. /cm ² , the pressure bonding time is preferably 5 seconds to 300 seconds, and the lamination is preferably performed under a reduced pressure of 20 mmHg or less. Moreover, the lamination process may be of a batch type or a continuous type using rolls. A vacuum lamination method can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. be able to.

Examples of substrates include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel and cold-rolled steel plate (SPCC); FR-4 substrates and the like; A heat-cured substrate; a substrate made of bismaleimide triazine resin such as BT resin; and the like.

Any material that can be peeled off from the semiconductor chip and that can temporarily fix the semiconductor chip can be used for the temporary fixing film. Commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

<Step (B)>
Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. Temporary fixing of the semiconductor chip can be performed using a device such as a flip chip bonder, a die bonder, or the like. The layout and the number of semiconductor chips to be arranged can be appropriately set according to the shape and size of the temporary fixing film, the target production volume of the semiconductor package, and the like. For example, the semiconductor chips may be arranged in a matrix of multiple rows and multiple columns and temporarily fixed.

<Step (C)>
Step (C) is a step of forming a sealing layer on the semiconductor chip. Any insulating material can be used for the sealing layer, and the resin composition of the present invention may be used. The encapsulating layer is usually formed by a method comprising the steps of forming a sealing resin composition layer on the semiconductor chip and thermally or photocuring the resin composition layer to form the encapsulating layer. do.

The formation of the encapsulating resin composition layer is preferably carried out by compression molding. In the compression molding method, the semiconductor chip and the encapsulating resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the encapsulating resin composition in the mold to seal the semiconductor chip. forming a resin composition layer for

The specific operation of the compression molding method can be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. In addition, the sealing resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the encapsulating resin composition is attached to the lower mold together with the substrate and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped, and heat and pressure are applied to the encapsulating resin composition for compression molding.

Also, the specific operation of the compression molding method may be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. A sealing resin composition is placed on the lower mold. Also, the semiconductor chip is attached to the upper mold together with the base material and the temporary fixing film. After that, the upper mold and the lower mold are clamped so that the sealing resin composition placed on the lower mold is in contact with the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

The molding conditions differ depending on the composition of the encapsulating resin composition, and suitable conditions can be adopted so as to achieve good encapsulation. For example, the temperature of the mold during molding is preferably a temperature at which the encapsulating resin composition can exhibit excellent compression moldability, 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. The pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, and preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The curing time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 5 minutes or longer, and preferably 60 minutes or shorter, more preferably 30 minutes or shorter, and particularly preferably 20 minutes or shorter. Usually, the mold is removed after forming the encapsulating resin composition layer. The mold may be removed before or after heat curing of the encapsulating resin composition layer.

The compression molding method may be performed by discharging the sealing resin composition filled in the cartridge into the lower mold.

<Step (D)>
Step (D) is a step of peeling off the substrate and the temporary fixing film from the semiconductor chip. As for the peeling method, it is desirable to employ an appropriate method according to the material of the temporary fixing film. Examples of the peeling method include a method of heating, foaming, or expanding the temporary fixing film to peel it. Moreover, as a peeling method, for example, a method of irradiating the temporary fixing film with ultraviolet rays through the base material to reduce the adhesive strength of the temporary fixing film and peel it off can be used.

In the method of peeling by heating, foaming or expanding the temporary fixing film, the heating conditions are usually 100° C. to 250° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. In the method of removing the temporary fixing film by irradiating with ultraviolet rays to reduce the adhesive strength of the temporary fixing film, the irradiation dose of ultraviolet rays is usually 10 mJ/cm ² to 1000 mJ/cm ² .

<Step (E)>
Step (E) is a step of forming a rewiring forming layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed. The resin composition of the present invention is used for the rewiring formation layer. The method for forming the rewiring formation layer is the same as the method for forming the resin composition layer in step (I) in the first embodiment.

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

The via hole is usually formed by exposing the surface of the resin composition layer for forming the rewiring layer through a mask pattern and irradiating actinic rays through a mask pattern, and developing and removing the non-exposed areas that are not irradiated with actinic rays. It can be formed by performing a developing step. The irradiation dose and irradiation time of actinic rays can be appropriately set according to the resin composition layer. Examples of the exposure method include a contact exposure method in which a mask pattern is brought into close contact with the resin composition layer for exposure, and a non-contact exposure method in which a mask pattern is not brought into close contact with the resin composition layer for exposure using parallel light rays. mentioned. The actinic ray, alkaline aqueous solution, and exposure/development method are as described above.

The shape of the via hole is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 20 μm or less, and preferably 0.1 μm or more, preferably 0.5 μm or more, and more preferably 1.0 μm or more. Here, the top diameter of the via hole means the diameter of the opening of the via hole on the surface of the rewiring 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 forming layer can be the same as the method of forming the conductor layer on the insulating layer in the first embodiment. Alternatively, the steps (E) and (F) may be repeated to alternately build up the rewiring layers and the rewiring formation layers (build-up).

<Step (G)>
Step (G) is a step of forming a solder resist layer on the rewiring layer. Any insulating material can be used as the material of the solder resist layer. Among them, photosensitive resins and thermosetting resins are preferable from the viewpoint of easiness in manufacturing semiconductor chip packages. Moreover, you may use the resin composition of this invention.

Also, in step (G), a bumping process for forming bumps may be performed as necessary. Bumping can be performed by a method such as solder balls or solder plating. Formation of via holes in the bumping process can be performed in the same manner as in step (E).

The method for manufacturing a semiconductor chip package may include step (H) in addition to steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into pieces. The method of dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited.

<Semiconductor device>
A semiconductor device of the present invention includes the semiconductor chip package of the present invention. Semiconductor devices mounted with semiconductor chip packages include, for example, electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (e.g., automatic (motorcycles, automobiles, trains, ships, aircraft, etc.).

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. The temperature condition is room temperature (23° C.) unless otherwise specified, and the pressure condition is atmospheric pressure (1 atm) unless otherwise specified. A weight average molecular weight is a weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography method.

21.8 g of 4,4'-difluorobenzophenone, 11.0 g of hydroquinone, and 15.1 g of potassium carbonate were placed in a 500 mL separable flask, 150 mL of N-methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature for 30 minutes under nitrogen. Stir for a minute. It was heated to 185° C. and polymerized for 3 hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 28 g of polyether resin (A). When the molecular weight of the polyether resin (A) was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 80,000.

31.8 g of the polyether resin (A) obtained in Comparative Example A1, 15.1 g of potassium carbonate, and 12.4 g of dimethylmethylphosphonate were dissolved in 150 mL of N-methylpyrrolidone and heated to 180° C. for 5 hours. Stirred. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 25 g of polyether resin (1). When the molecular weight of polyether resin (1) was measured by gel permeation chromatography (converted to 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

31.8 g of the polyether resin (A) obtained in Comparative Example A1, 15.1 g of potassium carbonate, and 22.8 g of diethylbenzylphosphonate were dissolved in 150 mL of N-methylpyrrolidone, heated to 180° C., and heated for 5 hours. Stirred. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 30 g of polyether resin (2).

31.8 g of the polyether resin (A) obtained in Comparative Example A1, 15.1 g of potassium carbonate, and 16.6 g of dimethyl(2-oxopropyl)phosphonate were dissolved in 150 mL of N-methylpyrrolidone and heated to 180°C. Warmed and stirred for 5 hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 25 g of polyether resin (3).

31.8 g of the polyether resin (A) obtained in Comparative Example A1, 15.1 g of potassium carbonate, and 16.6 g of trimethylphosphonoacetate were dissolved in 150 mL of N-methylpyrrolidone and heated to 180° C. Stirred for hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 29 g of polyether resin (4).

31.8 g of the polyether resin (A) obtained in Comparative Example A1, 15.1 g of potassium carbonate, 0.43 g of piperazine, and 13.2 g of dimethyl malonate were dissolved in 150 mL of N-methylpyrrolidone and heated to 140°C. Warmed and stirred for 5 hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating 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 so as to be 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 "X".

<Test Example A2: Measurement of dielectric constant (Dk) and dielectric loss tangent (Df)>
The polyether resin produced in each example and comparative example was added to N-methylpyrrolidone so as to be 10% by mass, and heated at 100° C. for 1 hour. Next, the dissolved polymer is placed on the release surface of a polyethylene terephthalate film with alkyd release treatment (PET film, “AL-5” manufactured by Lintec, thickness 38 μm), and the thickness of the resin layer after drying is 20 μm. , dried at 80 to 110 ° C. (95 ° C. on average) for 5 minutes, heated at 180 ° C. for 2 hours, and peeled off the PET film as a support to form a cured film. made.

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

Table 1 below shows 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.

21.8 g of 4,4′-difluorobenzophenone, 16.6 g of t-butylhydroquinone, and 15.1 g of potassium carbonate were placed in a 500 mL separable flask, 150 mL of N-methyl-2-pyrrolidone was added, and the mixture was stirred under nitrogen at room temperature. Stirred for 30 min. It was heated to 185° C. and polymerized for 3 hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating 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 (converted to standard polystyrene), the weight average molecular weight (Mw) was 150,000.

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, and 16.6 g of dimethyl(2-oxopropyl)phosphonate were dissolved in 150 mL of N-methylpyrrolidone and heated to 180°C. Warmed and stirred for 5 hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 31 g of polyether resin (6).

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, and 22.4 g of diethylmethylphosphonate were dissolved in 150 mL of N-methylpyrrolidone and heated to 180°C for 5 hours. Stirred. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 25 g of polyether resin (7).

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, and 16.6 g of triethylphosphonoacetate were dissolved in 150 mL of N-methylpyrrolidone and heated to 180° C. Stirred for hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating 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 (converted to 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

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, and 14.4 g of Meldrum's acid were dissolved in 150 mL of N-methylpyrrolidone, heated to 60° C., and stirred for 8 hours. did. 7.4 g of t-butyl alcohol was added and stirred at 130° C. for 2 hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 35 g 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 Meldrum's acid were dissolved in 150 mL of N-methylpyrrolidone, heated to 60° C., and stirred for 8 hours. did. 11.6 g of hydroxyethyl acrylate was added and stirred at 130° C. for 2 hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating 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 (converted to 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

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, 0.43 g of piperazine, and 13.2 g of dimethyl malonate were dissolved in 150 mL of N-methylpyrrolidone and heated to 140°C. Warmed and stirred for 5 hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 38 g of polyether resin (11).

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, 0.43 g of piperazine, and 15.6 g of diethyl malonate were dissolved in 150 mL of N-methylpyrrolidone and heated to 140°C. Warmed and stirred for 5 hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 38 g of polyether resin (12).

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, 0.43 g of piperazine, and 20.5 g of di-t-butylmalonate were dissolved in 150 mL of N-methylpyrrolidone and heated to 140°C. The mixture was warmed until it reached a temperature of 0.5% and stirred for 5 hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 38 g of polyether resin (13).

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, 0.43 g of piperazine, and 10.0 g of acetylacetone were dissolved in 150 mL of N-methylpyrrolidone and heated to 140°C. , and stirred for 5 hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 38 g of polyether resin (14).

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, 0.43 g of piperazine, and 13.8 g of dimedone were dissolved in 150 mL of N-methylpyrrolidone and heated to 140°C. , and stirred for 5 hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 39 g of polyether resin (15).

37.4 g of the polyether resin (B) obtained in Reference Example A1, 0.43 g of piperazine, and 14.4 g of Meldrum's acid were dissolved in 150 mL of N-methylpyrrolidone, heated to 60° C., and stirred for 10 hours. . Next, the resulting reaction solution was added dropwise to 2 L of acetone to precipitate a polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 40° C. to obtain 39 g of polyether resin (16).

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, 0.43 g of piperazine, and 12.8 g of ethyl acetoacetate were dissolved in 150 mL of N-methylpyrrolidone and heated to 140°C. Warmed and stirred for 5 hours. Next, the resulting reaction solution was added dropwise to 2 L of acetone to precipitate a polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 40° C. to obtain 35 g of polyether resin (17).

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, 0.43 g of piperazine, and 15.6 g of t-butyl acetoacetate are dissolved in 150 mL of N-methylpyrrolidone and heated to 140°C. and stirred for 5 hours. Next, the resulting reaction solution was added dropwise to 2 L of acetone to precipitate a polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 40° C. to obtain 37 g of polyether resin (18).

37.4 g of the polyether resin (B) obtained in Reference Example A1, 15.1 g of potassium carbonate, 0.43 g of piperazine, and 21.4 g of ethylene glycol monoacetoacetate monomethacrylate were dissolved in 150 mL of N-methylpyrrolidone and heated to 140°C. and stirred for 5 hours. Next, the resulting reaction solution was added dropwise to 2 L of acetone to precipitate a polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 40° C. to obtain 42 g of polyether resin (19). When the molecular weight of polyether resin (19) was measured by gel permeation chromatography (converted to standard polystyrene), 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

Tables 2 and 3 below show 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.

21.8 g of 4,4′-difluorobenzophenone, 35.5 g of BisP-CDE (bisphenol compound, manufactured by Honshu Kagaku Co., Ltd.), and 15.1 g of potassium carbonate were placed in a 500 mL separable flask, and N-methyl-2-pyrrolidone was added. 150 mL was added and stirred at room temperature for 30 minutes under nitrogen. It was heated to 185° C. and polymerized for 3 hours. Next, the resulting reaction solution was added dropwise to 2 L of ultrapure water to precipitate the polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating 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 (converted to 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

56.0 g of the polyether resin (C) obtained in Reference Example A2, 15.1 g of potassium carbonate, 0.43 g of piperazine, and 21.4 g of ethylene glycol monoacetoacetate monomethacrylate were dissolved in 150 mL of N-methylpyrrolidone and heated to 140°C. and stirred for 5 hours. Next, the resulting reaction solution was added dropwise to 2 L of acetone to precipitate a polymer for purification. After the purified polymer was separated by filtration, it was vacuum-dried under heating at 40° C. to obtain 58 g of polyether resin (20). When the molecular weight of the polyether resin (20) was measured by gel permeation chromatography (converted to standard polystyrene), 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

Table 4 below shows the measurement results and evaluation results of Test Examples A1 and A2 performed on the polyether resins obtained in Example A20 and Reference Example A2.

<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), an oxime ester photopolymerization initiator (manufactured by BASF "Irgacure- OXE02", [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate) 2 parts by mass, photosensitizer (1-phenyl-5-mercapto-1H-tetrazole , a photosensitizer represented by the following formula (5′)) was dissolved in 900 parts by mass of N-methylpyrrolidone to prepare a resin composition.

<Example B2>
A 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. prepared.

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

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

<Example B5>
A 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. prepared.

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

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

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

<Test Example B1: Evaluation of Limited Resolution (Resolution)>
The resin compositions obtained in Examples B1 to B5, Comparative Example B1, and Reference Examples B1 and B2 were plated with copper to a thickness of 10 μm on a silicon wafer, and subjected to coarsening treatment with a 1% hydrochloric acid aqueous solution for 10 seconds. A spin coater was used to coat the substrate at a rotation speed suitable for a film thickness of 10 μm, followed by heating on a hot plate at 120° C. for 5 minutes to prepare a resin composition layer. This is called a laminate.

The produced laminate was exposed to ultraviolet light (wavelength: 365 nm, intensity: 40 mW/cm ² ). The optimum exposure amount was set in the range of 50 mJ/cm ² to 1000 mJ/cm ² . As an exposure pattern, a quartz glass mask was used for drawing round holes (vias) 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 is sprayed with cyclopentanone as a developer at a spray pressure of 0.2 MPa for an optimum time of 30 seconds to 300 seconds, followed by acetic acid. Spray rinsing was performed with 2-methoxy-1-methylethyl (PGMEA) at a spray pressure of 0.2 MPa for 30 seconds. Further, heat treatment was performed at 180° C. for 120 minutes to cure the resin composition layer.

The diameters of the bottoms of vias with openings of 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 25 μm, and 30 μm in the exposure pattern of the cured resin composition layer were observed by SEM (1000x magnification) and measured. The minimum size that can be opened was taken as the resolution limit.

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

Table 5 below shows the content of each component of 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 application is based on Japanese Patent Application No. 2022-028105 (filed on February 25, 2022) filed with the Japan Patent Office, the entire contents of which are incorporated herein.

Claims

Formula (1):

[In the formula,
R 1 and R 2 each independently represent a hydrogen atom, —CN, —NO 2 , —COH, —R, —OR, —COR, —COOR, —CONHR, —CONR 2 , —SR, —SOR, or —SO 2 R, wherein R 1 and R 2 may combine together to form a non-aromatic ring which may have a substituent;
R each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
R 3 and R 4 each independently represent a substituent;
Ring X 1 and Ring X 2 each independently represent an aromatic carbocyclic ring which may have a substituent;
Y represents a single bond or an organic group;
a represents 0 or 1;
p and q each independently represent 0, 1, 2, 3, or 4; ]
Polyether resin having a repeating unit represented by.
Formula (3):

[In the formula,
R 1 and R 2 each independently represent a hydrogen atom, —R, —COR, or —COOR, and R 1 and R 2 are bonded together to form an optionally substituted non- may form an aromatic ring;
R each independently represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group;
R 3 , R 4 , R 5 and R 6 each independently represent a substituent;
RA and RB each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group, and RA and RB together may be combined to form a non-aromatic ring optionally having a substituent;
a and b each independently represent 0 or 1;
p, q, r and s each independently represent 0, 1, 2, 3 or 4; ]
2. The polyether resin according to claim 1, which has a repeating unit represented by
If a is 0,
s is 1 or more, and at least one of R 6 is an alkyl group having 4 or more carbon atoms;
If a is 1 and b is 0,
the sum of r and s is 1 or more, and at least one of R 5 and R 6 is an alkyl group having 4 or more carbon atoms;
If a is 1 and b is 1,
(1) the sum of r and s is 1 or more, and at least one of R 5 and R 6 is an alkyl group having 4 or more carbon atoms, and/or (2-1) R A and R B are represents a hydrogen atom or an alkyl group, and at least one of which is an alkyl group having 4 or more carbon atoms, or (2-2) R A and R B are bonded together and substituted with an alkyl group Forms a 5-membered or more monocyclic non-aromatic saturated carbocyclic ring that may be optionally substituted with an alkyl group, or a 6-membered or more bicyclic or more non-aromatic saturated carbocyclic ring that may be substituted with an alkyl group, according to claim 2 The polyether resin described.
The polyether resin according to claim 1, which has a weight average molecular weight of 5,000 or more.
The polyether resin according to claim 1, wherein the dielectric loss tangent (Df) is 0.012 or less when measured at 5.8 GHz and 23°C.
An insulating material containing the polyether resin according to claim 1.
A resin composition comprising the polyether resin according to claim 1 and a curable cross-linking agent.
A resin composition comprising the polyether resin according to claim 1, a photocurable cross-linking agent, and a photopolymerization initiator.
The resin composition according to claim 8, further comprising a photosensitizer.
A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of claims 7 to 9 provided on the support.
A semiconductor package substrate comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 7 to 9.
A semiconductor device, comprising the semiconductor package substrate according to claim 11.
A method for manufacturing a semiconductor package substrate including the following steps (I) to (III) in this order.
(I) Step of forming a resin composition layer formed of the resin composition according to claim 8 or 9 on a circuit board (II) Step of irradiating the resin composition layer with actinic rays (III) Resin composition the process of developing the layer