Method for producing polyester resin

Abstract

To provide a technique for production of polyester resin that can reduce trouble in an oil-water separation step when producing polyester resin, particularly rigid-structure active ester resin, and also employs a safe reaction solvent, and further provide a technique for production of a resin composition containing the polyester resin.SOLUTION: A method for producing polyester resin is provided. In a condensation of an acid halide compound and an aromatic hydroxy compound, at least one solvent A selected from the group consisting of cycloalkyl alkylether and alkyl tetrahydropyran is used as a reaction solvent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing a polyester resin. Further, it relates to a resin crosslinking agent, a resin composition, a sheet-like laminated material, a printed wiring board, a semiconductor chip package, and a semiconductor device obtained by using the polyester resin produced by the method.

Background Art

[0002] Resin compositions containing a crosslinkable resin such as an epoxy resin and its crosslinking agent (curing agent) have been widely used as electronic component materials such as semiconductors and printed wiring boards because they provide cured products with excellent insulation, heat resistance, adhesion, etc.

[0003] On the other hand, in high-speed communication such as the fifth-generation mobile communication system (5G), transmission loss when operating in a high-frequency environment becomes a problem. Therefore, an insulating material having excellent dielectric properties (low dielectric constant, low dielectric tangent) is required. As an insulating material that realizes good dielectric properties, for example, Patent Documents 1 and 2 disclose resin compositions containing an active ester resin.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] The active ester resin is an aromatic polyester resin and is essentially poorly soluble in organic solvents. As a method for producing an aromatic polyester resin, a condensation reaction between an acid halide compound and an aromatic hydroxy compound using a hydrophobic organic solvent as a reaction solvent is common, but many of the resulting aromatic polyester resins have low solubility in the reaction solvent. Among them, the rigid backbone type active ester resin, which has an excellent balance between dielectric properties and heat resistance, has particularly low solubility in the reaction solvent.

[0006] In addition, for this condensation reaction, dehydrohalogenating agents such as alkalis and amines are used, but a large amount of by-product salts are generated during the reaction. In order to discharge the by-product salts out of the reaction system, it is necessary to add water and perform water washing purification. However, when using a reaction solvent with low solubility, the oil-water separability deteriorates, leading to serious problems such as the disappearance of the liquid-liquid separation interface or the formation of a large amount of emulsion intermediate layer.

[0007] On the other hand, aromatic solvents such as toluene and xylene, which are representative of hydrophobic organic solvents used as reaction solvents, and ketone solvents such as methyl isobutyl ketone (MIBK) are being increasingly regulated from the perspective of safety, making their use difficult.

[0008] Furthermore, the resin composition containing the active ester resin is processed into a film or a coating agent for thinning, and in this case, it is necessary to add an organic solvent to prepare a varnish-like resin composition. For such an organic solvent as well, a highly safe and highly soluble solvent is required.

[0009] The present invention provides a polyester resin manufacturing technology, and further a resin composition manufacturing technology containing the polyester resin, which can improve the problems in the oil-water separation process and use a more safe reaction solvent when manufacturing a polyester resin, particularly a rigid backbone type active ester resin.

Means for Solving the Problems

[0010] As a result of intensive studies to solve the above problems, the present inventors have found that by using a solvent selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans as a reaction solvent, problems in the production process can be significantly improved, and a method for producing a polyester resin that highly considers safety can be provided. Furthermore, it has been found that the above specific solvent is also useful as an organic solvent when producing a varnish-like resin composition, and the present invention has been completed.

[0011] That is, the present invention includes the following. [1] A method for producing a polyester resin, wherein in the condensation reaction of an acid halide compound and an aromatic hydroxy compound, at least one solvent A selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans is used as the reaction solvent. [2] The method for producing a polyester resin according to [1], wherein the polyester resin contains an active ester group. [3] The method for producing a polyester resin according to [1] or [2], wherein the acid halide compound is divalent and the aromatic hydroxy compound is a mixture of monovalent and divalent. [4] The method for producing a polyester resin according to [1] or [2], wherein the acid halide compound is a mixture of monovalent and divalent and the aromatic hydroxy compound is divalent. [5] The method for producing a polyester resin according to any one of [1] to [4], wherein the molar ratio of the halide group to the aromatic hydroxy group is in the range of the former: the latter = 1.00: 0.80 to 1.00: 1.20. [6] The method for producing a polyester resin according to any one of [1] to [5], wherein the polyester resin contains an average of 2 to 10 active ester groups per molecule. [7] The method for producing a polyester resin according to any one of [1] to [6], wherein the boiling point of the solvent A is in the range of 70 to 150 °C. [8] The method for producing a polyester resin according to any one of [1] to [7], wherein the cycloalkyl alkyl ether is represented by the following formula (1) and the alkyl tetrahydropyran is represented by the following formula (2). [Chemical formula] (In the formula, R 11 represents a cycloalkyl group having 3 to 10 carbon atoms, R 12 represents an alkyl group having 1 to 6 carbon atoms.) [Chemical formula] (In the formula, R 21 represents an alkyl group having 1 to 6 carbon atoms.) [9] The method for producing a polyester resin according to any one of [1] to [8], wherein the solvent A contains cyclopentyl methyl ether, cyclohexyl methyl ether, or 4-methyltetrahydropyran.

[10] The method for producing a polyester resin according to any one of [1] to [9], wherein the addition amount of the solvent A is 30 to 500% by mass based on 100% by mass of the total amount of the acid halide compound and the aromatic hydroxy compound.

[11] The following steps (1) to (4): (1) A step of dissolving an acid halide compound and an aromatic hydroxy compound in at least one solvent A selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans to obtain a solution; (2) A step of adding a dehydrohalogenating agent to the solution to carry out a condensation reaction; (3) After the condensation reaction, a step of adding water and separating the oil and water to discharge the by-produced salt out of the system; and (4) A step of further purifying by washing with water and separating the oil and water The method for producing a polyester resin according to any one of [1] to

[10] , comprising.

[12] The following steps (5) and (6): (5) A step of performing a dehydration treatment to precipitate a by-produced salt; and (6) A step of removing the by-produced salt by filtration The method for producing a polyester resin according to

[11] , further comprising.

[13] A resin crosslinking agent containing (A) a polyester resin and one or more solvents selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans.

[14] A resin crosslinking agent containing the polyester resin obtained by the production method according to any one of [1] to

[12] and solvent A used as a reaction solvent.

[15] A resin composition containing (A) a polyester resin, (B) one or more solvents selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans, and (C) a crosslinkable resin.

[16] A resin composition containing the polyester resin obtained by the production method according to any one of [1] to

[12] , solvent A used as a reaction solvent, and a crosslinkable resin.

[17] The resin composition according to

[15] or

[16] , further containing an inorganic filler.

[18] The resin composition according to any one of

[15] to

[17] , which is for an insulating layer of a printed wiring board.

[19] The resin composition according to any one of

[15] to

[17] , which is for semiconductor encapsulation.

[20] A sheet-like laminated material containing the resin composition according to any one of

[15] to

[19] .

[21] A printed wiring board including an insulating layer made of a cured product of the resin composition according to any one of

[15] to

[18] .

[22] A semiconductor chip package including a sealing layer made of a cured product of the resin composition according to any one of

[15] to

[17] ,

[19] .

[23] The semiconductor chip package according to

[22] , which is a fan-out type package.

[24] A semiconductor device including the printed wiring board according to

[21] or the semiconductor chip package according to

[22] or

[23] .

Advantages of the Invention

[0012] According to the present invention, in the production of a polyester resin, particularly a rigid backbone active ester resin, it is possible to improve problems in the oil-water separation step and use a highly safe reaction solvent, thereby providing a production technique for a polyester resin and further a production technique for a resin composition containing the polyester resin.

Embodiments for Carrying Out the Invention

[0013] Hereinafter, the present invention will be described in detail in accordance with its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0014] [Method for Producing Polyester Resin] The method for producing a polyester resin of the present invention (hereinafter, also simply referred to as "the production method of the present invention") is characterized in that, in the condensation reaction between an acid halide compound and an aromatic hydroxy compound, at least one solvent A selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans is used as the reaction solvent.

[0015] As described above, aromatic polyester resins such as active ester resins essentially have poor solubility in organic solvents, and during oil-water separation in the production process, serious problems such as the disappearance of the liquid-liquid interface and the formation of a large amount of emulsion intermediate layers may occur. Among them, rigid backbone active ester resins having an aromatic polycyclic skeleton have particularly low solubility in reaction solvents, and problems in the production process tend to be more prominent.

[0016] In contrast, according to the production method of the present invention using Solvent A as a reaction solvent, even when producing a rigid skeleton type active ester resin, problems in the production process can be significantly improved. Coupled with the fact that Solvent A is safer than toluene, MIBK, etc. that have been conventionally used as reaction solvents, the present invention significantly contributes to providing a polyester resin production technology that highly considers safety aspects while significantly improving problems in the production process.

[0017] - Solvent A - Solvent A is one or more selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans.

[0018] From the viewpoint of easily distilling off Solvent A after the production of the polyester resin, the boiling point of Solvent A is preferably 150°C or lower, more preferably 140°C or lower. The lower limit of the boiling point is not particularly limited, but from the viewpoint of avoiding extreme volatilization, such as when using Solvent A as a solvent in the production of a varnish-like resin composition containing a polyester resin, it is preferably 70°C or higher, more preferably 80°C or higher, 90°C or higher, or 100°C or higher. Therefore, in one embodiment, the boiling point of Solvent A is in the range of 70 to 150°C.

[0019] The cycloalkyl alkyl ether used as Solvent A is preferably represented by the following formula (1).

[0020] [Chemical formula] (In the formula, R 11 represents a cycloalkyl group having 3 to 10 carbon atoms, and R 12 represents an alkyl group having 1 to 6 carbon atoms.)

[0021] In formula (1), R 11represents a cycloalkyl group having 3 to 10 carbon atoms. The number of carbon atoms in the cycloalkyl group is more preferably 4 or more, even more preferably 5 or more, and the upper limit is more preferably 8 or less, even more preferably 7 or less or 6 or less.

[0022] In formula (1), R 12 represents an alkyl group having 1 to 6 carbon atoms. The number of carbon atoms in the alkyl group is more preferably 4 or less, even more preferably 3 or less.

[0023] Among them, even in the case of producing a rigid skeleton type active ester resin, from the viewpoint of significantly improving the problems in the production process, as the cycloalkylalkyl ether represented by formula (1), cyclopentyl C 1-3 alkyl ether and cyclohexyl C 1-3 alkyl ether are preferred, and cyclopentylmethyl ether and cyclohexylmethyl ether are particularly preferred.

[0024] The alkyltetrahydropyran used as solvent A is preferably represented by the following formula (2).

[0025]

Chemical formula

[0026] In formula (2), R 21 represents an alkyl group having 1 to 6 carbon atoms. The number of carbon atoms in the alkyl group is more preferably 4 or less, even more preferably 3 or less.

[0027] In formula (2), the bonding position of the alkyl group represented by R 21 is not particularly limited and may be any of the 2-position, 3-position, and 4-position.

[0028] Among them, even in the case of producing a rigid skeleton type active ester resin, from the viewpoint of significantly improving defects in the production process, as the alkyltetrahydropyran represented by the formula (2), 4-C 1-3 alkyltetrahydropyran is preferable, and 4-methyltetrahydropyran is particularly preferable.

[0029] In a preferred embodiment, the solvent A contains cyclopentyl methyl ether, cyclohexyl methyl ether, or 4-methyltetrahydropyran.

[0030] In the production method of the present invention, from the viewpoint of improving defects in the production process, the concentration of the solvent A in the reaction solvent is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more, even more preferably 90% by mass or more or 95% by mass or more, and may be 100% by mass (the reaction solvent is only the solvent A).

[0031] -Condensation reaction of acid halide compound and aromatic hydroxy compound- In the production method of the present invention, the polyester resin is produced by a condensation reaction (esterification reaction) of an acid halide compound and an aromatic hydroxy compound.

[0032] According to the production method of the present invention using the above solvent A as the reaction solvent, regardless of the type of the polyester resin, it is possible to achieve good oil-water separability in its production process, specifically in the oil-water separation process. From the viewpoint of more enjoying such an effect of the present invention, the polyester resin to be produced is preferably an active ester resin, that is, a polyester resin containing an active ester group, which tends to have defects in the oil-water separation process. In the present invention, the "active ester group" refers to an ester bond portion having a structure of aromatic carbon -C(=O)-O- aromatic carbon, and also includes an ester bond portion having a structure of aliphatic carbon -C(=O)-O- aromatic carbon as long as the crosslinking characteristics of the crosslinkable resin are exhibited. Therefore, in a preferred embodiment, the polyester resin contains an active ester group.

[0033] In the production method of the present invention, from the viewpoint of fully expressing the crosslinking characteristics of the crosslinkable resin, the polyester resin to be produced preferably contains an average of 2 to 10 active ester groups per molecule.

[0034] As described above, among the active ester resins, the rigid skeleton type active ester resin having an aromatic polycyclic skeleton tended to have more prominent problems in the production process. In this regard, according to the production method of the present invention using the above solvent A as the reaction solvent, even when producing a rigid skeleton type active ester resin having an aromatic polycyclic skeleton, the problems in the production process can be significantly improved. The aromatic polycyclic skeleton refers to a skeleton containing two or more cyclic structures, and at least one of the cyclic structures is an aromatic ring. The two or more cyclic structures may or may not be condensed. The aromatic polycyclic skeleton may be any conventionally known aromatic polycyclic skeleton constituting the rigid skeleton type active ester resin. For example, an aromatic hydrocarbon skeleton in which aromatic rings such as a naphthalene skeleton and an anthracene skeleton are condensed; an aromatic hydrocarbon skeleton (non-condensed type aromatic hydrocarbon skeleton) contained without condensation, such as two or more aromatic rings such as a biphenyl skeleton being bonded by a single bond; an aromatic hydrocarbon skeleton in which a 5-membered ring compound such as an indane skeleton including a 1,1,3-trimethylindane skeleton and a fluorene skeleton are condensed with an aromatic ring, etc. are mentioned. Therefore, in a preferred embodiment, the polyester resin is an active ester resin having an aromatic polycyclic skeleton.

[0035] In the production method of the present invention, the acid halide compound and the aromatic hydroxy compound may be of any type as long as a polyester resin can be produced by their condensation reaction. The acid halide compound is not particularly limited as long as it contains at least a part of a polyvalent acid halide compound. Depending on the structure of the target polyester resin, only a polyvalent acid halide compound may be used, or a mixture of a monovalent acid halide compound and a polyvalent acid halide compound may be used. Similarly, the aromatic hydroxy compound is not particularly limited as long as it contains at least a part of a polyvalent aromatic hydroxy compound. Depending on the structure of the target polyester resin, only a polyvalent aromatic hydroxy compound may be used, or a mixture of a monovalent aromatic hydroxy compound and a polyvalent aromatic hydroxy compound may be used.

[0036] In a preferred embodiment, a divalent acid halide compound is used as the acid halide compound, and a mixture of a monovalent aromatic hydroxy compound and a divalent aromatic hydroxy compound is used as the aromatic hydroxy compound. That is, the acid halide compound is divalent, and the aromatic hydroxy compound is a mixture of monovalent and divalent. In such an embodiment, the terminal structure tends to result in a polyester resin derived from the monovalent aromatic hydroxy compound.

[0037] In another preferred embodiment, a mixture of a monovalent acid halide compound and a divalent acid halide compound is used as the acid halide compound, and a divalent aromatic hydroxy compound is used as the aromatic hydroxy compound. That is, the acid halide compound is a mixture of monovalent and divalent, and the aromatic hydroxy compound is divalent. In such an embodiment, the terminal structure tends to result in a polyester resin derived from the monovalent acid halide compound.

[0038] Hereinafter, an example of the acid halide compound and the aromatic hydroxy compound that can be preferably used in the production method of the present invention will be shown. As described above, according to the production method of the present invention using solvent A as the reaction solvent, an acid halide compound having an aromatic polycyclic skeleton (R in the following formula (3)) a1when it contains an aromatic polycyclic skeleton) or an aromatic hydroxy compound having an aromatic polycyclic skeleton (R in the following formula (5)) b1 -[L-R b1 n even when producing a rigid skeleton type active ester resin using a case where the [L-R] part contains an aromatic polycyclic skeleton), problems in the production process can be significantly improved.

[0039] -- Acid halide compound -- As the divalent acid halide compound, preferably a compound represented by the following formula (3) can be mentioned.

[0040] [Chemical formula] (In the formula, R a1 represents a divalent aromatic group or a divalent aliphatic group, Z represents a halogen atom.)

[0041] R a1 The divalent aromatic group represented by is preferably an arylene group which may have a substituent. The number of carbon atoms of the arylene group in R a1 is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms. In a preferred embodiment, the divalent aromatic group represented by R a1 is a phenylene group which may have a substituent or a naphthylene group which may have a substituent, and more preferably a phenylene group which may have a substituent. Further, as the substituent which the arylene group in R a1 may have, one or more selected from a halogen atom, an alkyl group, and an aryl group are preferable, and one or more selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms are more preferable.

[0042] R a1 The divalent aliphatic group represented by is preferably an alkylene group which may have a substituent or an alkenylene group which may have a substituent. R​a1 The alkylene group or alkenylene group in may be either linear or branched. R a1 The number of carbon atoms of the divalent aliphatic group represented by is preferably 4 or more, more preferably 6 or more or 8 or more, and the upper limit is not particularly limited, but may usually be 30 or less, 20 or less, 18 or less, etc. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Also, R a1 As the substituent that the alkylene group or alkenylene group in may have, one or more selected from a halogen atom, an alkyl group, and an aryl group are preferable, and one or more selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms are more preferable.

[0043] Examples of the halogen atom represented by Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.

[0044] As described above, the divalent acid halide compound may be appropriately determined according to the structure of the target polyester resin. Preferable specific examples of the divalent acid halide compound include isophthalic acid chloride which may have a substituent, terephthalic acid chloride which may have a substituent, suberic acid chloride which may have a substituent, sebacic acid chloride which may have a substituent, and the like.

[0045] As the monovalent acid halide compound, preferably a compound represented by the following formula (4) is mentioned.

[0046]

Chemical formula

[0047] R a2 The monovalent aromatic group represented by is preferably an aryl group which may have a substituent. R a2The number of carbon atoms of the aryl group is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms. In a preferred embodiment, R a2 The monovalent aromatic group represented by is a phenyl group which may have a substituent or a naphthyl group which may have a substituent. Also, R a2 As the substituent that the aryl group in may have, one or more selected from a halogen atom, an alkyl group, and an aryl group are preferable, and one or more selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms are more preferable.

[0048] R a2 The monovalent aliphatic group represented by is preferably an alkyl group which may have a substituent or an alkenyl group which may have a substituent. The alkyl group or alkenyl group in R a2 may be either linear or branched. The number of carbon atoms of the divalent aliphatic group represented by R a2 is preferably 4 or more, more preferably 6 or more or 8 or more, and the upper limit is not particularly limited, but may usually be 30 or less, 20 or less, 18 or less, etc. Also, as the substituent that the alkyl group or alkenyl group in R a2 may have, one or more selected from a halogen atom, an alkyl group, and an aryl group are preferable, and one or more selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms are more preferable.

[0049] The monovalent acid halide compound may be appropriately determined according to the structure of the target polyester resin as described above. Preferable specific examples of the monovalent acid halide compound include benzenecarboxylic acid chloride which may have a substituent, naphthalenecarboxylic acid chloride which may have a substituent, caproic acid chloride which may have a substituent, enanthic acid chloride which may have a substituent, caprylic acid chloride which may have a substituent, and the like.

[0050] --Aromatic hydroxy compound-- Examples of the divalent aromatic hydroxy compound preferably include a compound represented by the following formula (5).

[0051] [Chemical formula] (In the formula, R b1 each independently represents a divalent aromatic group, L each independently represents a single bond or a divalent linking group, n represents an integer of 0 to 5.)

[0052] R b1 The divalent aromatic group represented by is preferably an arylene group which may have a substituent. The number of carbon atoms of the arylene group in R b1 is preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms. In a preferred embodiment, the divalent aromatic group represented by R b1 is a phenylene group which may have a substituent or a naphthylene group which may have a substituent, and more preferably a phenylene group which may have a substituent. Further, as the substituent which the arylene group in R b1 may have, one or more selected from a halogen atom, an alkyl group, an aryl group, and an arylalkyl group are preferable, and one or more selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an arylalkyl group (aryl group having 6 to 10 carbon atoms, alkyl group having 1 to 6 carbon atoms) are more preferable. The arylene group in R b1 may have a hydroxy group as a substituent. In such a case, the valence of the aromatic hydroxy compound represented by the formula (5) may exceed 2.

[0053] L represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L include divalent organic groups composed of one or more (e.g., 1 to 3000, 1 to 1000, 1 to 100, 1 to 50) skeletal atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. Among them, a divalent aliphatic group which may have a substituent or a divalent aromatic group which may have a substituent is preferable.

[0054] Examples of the divalent aliphatic group in L include an alkylene group, a cycloalkylene group, an alkenylene group, a cycloalkenylene group, an alkapolyenylene group (the number of double bonds is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and even more preferably 2), etc. An alkylene group, a cycloalkylene group, an alkenylene group, and a cycloalkenylene group are preferable, an alkylene group and a cycloalkylene group are more preferable, and a cycloalkylene group is still more preferable. The number of carbon atoms of the divalent aliphatic group in L is not particularly limited. For example, when the divalent aliphatic group is a cycloalkylene group, the number of its carbon atoms is preferably 3 to 15, more preferably 3 to 12, and still more preferably 3 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms.

[0055] Examples of the divalent aromatic group in L include an arylene group and a heteroarylene group, with the arylene group being preferred. The number of carbon atoms in the arylene group in L is preferably from 6 to 24, more preferably from 6 to 18, and still more preferably from 6 to 14. The number of carbon atoms of substituents is not included in this carbon atom count. Examples of the arylene group include a phenylene group, a naphthylene group, an anthracenylene group, a fluorenediyl group (e.g., 9H-fluorene-9,9-diyl group), a phenanthrenediyl group, an indanediyl group, a pyrenediyl group, and the like. The number of carbon atoms in the heteroarylene group in L is preferably from 3 to 21, more preferably from 3 to 15, and still more preferably from 3 to 9. The number of carbon atoms of substituents is not included in this carbon atom count. Examples of the heteroarylene group include a pyrrolediyl group, a furandiyl group, a thiophenediyl group, a pyridinediyl group, a pyridazinediyl group, a pyrimidinediyl group, a pyrazinediyl group, a triazinediyl group, and the like.

[0056] Examples of the substituent that the divalent group represented by L may have include one or more selected from a halogen atom, an alkyl group, and an aryl group, with one or more selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms being more preferred.

[0057] n is an integer from 0 to 5, preferably an integer from 0 to 3, and more preferably an integer from 0 to 2.

[0058] The divalent aromatic hydroxy compound may be appropriately determined according to the structure of the target polyester resin as described above. Examples of the divalent aromatic hydroxy compound include, as a component where n is 1 or more, a polyaddition reaction product of an unsaturated aliphatic cyclic compound containing two double bonds in one molecule and phenols, various bisphenol compounds, and the like. Examples of the polyaddition reaction product of the unsaturated aliphatic cyclic compound and phenols include polyaddition reaction products of unsaturated aliphatic cyclic compounds such as dicyclopentadiene, tetrahydroindene, norbornadiene, limonene, vinylcyclohexene, etc. and phenols which may have a substituent (for example, phenol, cresol, xylenol, ethylphenol, propylphenol, vinylphenol, allylphenol, phenylphenol, benzylphenol, halophenol, etc.), and specifically, for example, dicyclopentadiene-phenol polyaddition product and the like. Examples of the bisphenol compound include bisphenol fluorene, bisphenol A, bisphenol F, bisphenol AF, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, bisphenol M, etc. Further, as a component where n is 0, diols (such as benzenediol, naphthalenediol, etc.) in which two hydroxy groups are bonded to carbon atoms on the aromatic ring can be mentioned.

[0059] Examples of the monovalent aromatic hydroxy compound preferably include a compound represented by the following formula (6).

[0060] [Chemical formula] (In the formula, R b2 represents a monovalent aromatic group.)

[0061] R b2 The monovalent aromatic group represented by is preferably an aryl group which may have a substituent. R a2The number of carbon atoms in the aryl group is preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. The number of carbon atoms of the substituent is not included in the number of carbon atoms. In a preferred embodiment, R a2 The monovalent aromatic group represented by is a phenyl group which may have a substituent or a naphthyl group which may have a substituent. Also, R a2 As the substituent that the aryl group in may have, one or more selected from a halogen atom, an alkyl group, and an aryl group are preferable, and one or more selected from a fluorine atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms are more preferable.

[0062] The monovalent aromatic hydroxy compound may be appropriately determined according to the structure of the target polyester resin as described above. Examples of the monovalent aromatic hydroxy compound include naphthol which may have a substituent, phenol which may have a substituent, and the like.

[0063] In the production method of the present invention, the acid halide compound and the aromatic hydroxy compound are preferably used in an amount ratio such that the molar ratio of the halide group to the aromatic hydroxy group (the former: the latter) is in the range of 1.00:0.80 to 1.00:1.20, and more preferably in an amount ratio such that the molar ratio is in the range of 1.00:0.90 to 1.00:1.10.

[0064] When a mixture of a monovalent and a divalent compound is used as the acid halide compound, the amount ratio of the monovalent compound to the divalent compound may be appropriately determined according to the structure of the target polyester resin. For example, the molar ratio of the halide group derived from the monovalent compound to the halide group derived from the divalent compound (the former: the latter) is preferably used in an amount ratio such that the molar ratio is in the range of 1.00:0.80 to 1.00:10.00, and more preferably in an amount ratio such that the molar ratio is in the range of 1.00:0.90 to 1.00:5.00. When the amount ratio of the halide group derived from the divalent compound to the halide group derived from the monovalent compound increases, the degree of condensation of the polyester resin tends to increase.

[0065] In addition, when using a mixture of monovalent and divalent aromatic hydroxy compounds, the amount ratio of the monovalent compound to the divalent compound may be appropriately determined according to the structure of the target polyester resin. For example, it is preferably used in an amount ratio such that the molar ratio of the aromatic hydroxy group derived from the monovalent compound to the aromatic hydroxy group derived from the divalent compound (the former: the latter) is in the range of 1.00:0.80 to 1.00:10.00, and more preferably in an amount ratio such that the range is 1.00:0.90 to 1.00:5.00. When the amount ratio of the aromatic hydroxy group derived from the divalent compound to the aromatic hydroxy group derived from the monovalent compound increases, the degree of condensation of the polyester resin tends to increase.

[0066] In the production method of the present invention, the addition amount of the solvent A used as the reaction solvent is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, 80% by mass or more, or 100% by mass or more with respect to 100% by mass of the total amount of the acid halide compound and the aromatic hydroxy compound, and the upper limit thereof is preferably 500% by mass or less, more preferably 450% by mass or less, still more preferably 400% by mass or less. Therefore, in a preferred embodiment, the addition amount of the solvent A is 30 to 500% by weight with respect to 100% by mass of the total amount of the acid halide compound and the aromatic hydroxy compound.

[0067] In the condensation reaction, a dehydrohalogenating agent may be used. As the dehydrohalogenating agent, any conventionally known one such as alkalis and amines may be used. For example, alkali metal hydroxides such as sodium hydroxide (caustic soda) and potassium hydroxide; tertiary amines such as triethylamine, pyridine, N,N-dimethyl-4-aminopyridine (DMAP), etc. may be mentioned. The dehydrohalogenating agent may be used alone or in combination of two or more. In addition, the addition amount of the dehydrohalogenating agent is not particularly limited as long as the condensation reaction can proceed, and may be appropriately determined according to the type thereof.

[0068] In the condensation reaction, an interlayer transfer catalyst may also be used. Any conventionally known catalyst that can be used in the esterification reaction may be used.

[0069] The reaction temperature in the condensation reaction is not particularly limited as long as the condensation reaction proceeds, and may be, for example, in the range of 0 to 80°C. The reaction time in the condensation reaction is not particularly limited as long as the structure of the target polyester resin is achieved, and may be, for example, in the range of 30 minutes to 8 hours.

[0070] The polyester resin may be purified after the condensation reaction. For example, after the condensation reaction, in order to remove by-produced salts and excess starting materials from the system, purification steps such as washing with water and microfiltration may be performed. Specifically, after the condensation reaction, an amount of water necessary to dissolve the by-produced salts is added, and the aqueous layer containing the by-produced salts is discharged out of the system by oil-water separation. Further, the operation of discharging the aqueous layer containing the by-produced salts out of the system by washing with water and performing oil-water separation may be repeated. In such an operation of washing with water and oil-water separation, an acid may be added and neutralized as necessary. As the acid used for neutralization, any conventionally known one such as sodium hydrogen phosphate may be used. Thereafter, after passing through a dehydration step by a chemical or azeotropic distillation and performing microfiltration to remove impurities and purification, if necessary, the polyester resin can be obtained by distilling off the reaction solvent.

[0071] In a preferred embodiment, the production method of the present invention comprises the following steps (1) to (4): (1) A step of dissolving an acid halide compound and an aromatic hydroxy compound in at least one solvent A selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans to obtain a solution; (2) A step of adding a dehydrohalogenating agent to the solution to carry out a condensation reaction; (3) After the condensation reaction, a step of adding water and performing oil-water separation to discharge the by-produced salts out of the system; and (4) A step of further purifying by washing with water and performing oil-water separation is included.

[0072] The solvent A, acid halide compound, and aromatic hydroxy compound used in step (1) are as described above, and their quantitative ratios are also as previously described. The method of dissolving in solvent A is not particularly limited as long as the acid halide compound and aromatic hydroxy compound can be dissolved, and it may be dissolved by appropriately heating with stirring, for example. When heating, the liquid temperature may be in the range of, for example, 20 to 40°C. In the production method of the present invention using solvent A, the acid halide compound and aromatic hydroxy compound can be easily dissolved to obtain a solution.

[0073] The dehydrohalogenating agent used in step (2) is as described above, and the reaction temperature and time of the condensation reaction are also as previously described.

[0074] In step (3), water is added to the reaction solution after the condensation reaction to perform oil-water separation. Then, by discarding the aqueous layer, the by-produced salt can be discharged out of the system. As described above, in the production method of the present invention using solvent A, problems such as disappearance of the liquid separation interface and formation of a large amount of emulsion intermediate layer during oil-water separation can be significantly reduced. Thereby, the by-produced salt can be efficiently discharged out of the system, and the target polyester resin can be obtained with good yield. In addition, combined with the fact that solvent A has higher safety than toluene, MIBK, etc. that have been conventionally used as reaction solvents, the present invention can greatly improve the problems in the production process and also highly consider the safety aspect.

[0075] The washing with water and oil-water separation in step (4) may be carried out in the same manner as in step (3). Also, as previously described, an acid may be added and neutralized as necessary during the washing with water and oil-water separation.

[0076] In a preferred embodiment, the production method of the present invention, in addition to the above steps (1) to (4), further includes the following steps (5) and (6): (5) A step of performing dehydration treatment to precipitate the by-produced salt; and (6) A step of removing the by-produced salt by filtration is further included.

[0077] In step (5), the dehydration treatment may be carried out by using a chemical agent (dehydrating agent) or azeotropic distillation as described above. When using a dehydrating agent, any conventionally known dehydrating agent such as magnesium sulfate may be used.

[0078] In step (6), the filtration may be carried out by using any method capable of filtering the precipitated by-product salt generated in step (5), preferably by using microfiltration with a microfiltration membrane. The material of the microfiltration membrane and the size of the filtration pores are not particularly limited as long as the precipitated by-product salt can be sufficiently filtered off, and any conventionally known material and size may be selected and determined.

[0079] As described above, after removing the by-product salt, the polyester resin can be obtained by distilling off the reaction solvent. Here, in the production method of the present invention using the above solvent A as the reaction solvent, the reaction solvent may not be removed or only a part of it may be removed and used as it is as the solvent of the resin composition. Since solvent A volatilizes under normal film-forming conditions, it is also useful as solvent A constituting the varnish-like resin composition, and since it has high safety as described above, a varnish-like resin composition highly considered from the viewpoint of safety can be realized.

[0080] [Resin cross-linking agent] The polyester resin obtained by the production method of the present invention can be suitably used as a resin cross-linking agent. The present invention also provides such a resin cross-linking agent.

[0081] In one embodiment, the resin cross-linking agent of the present invention contains (A) a polyester resin and one or more solvents selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans.

[0082] (A) component, the polyester resin, is as described in the [Method for Producing Polyester Resin] section above, including acid halide compounds and aromatic hydroxy compounds as raw materials. From the perspective of blending and using it in the resin composition as a resin crosslinking agent, the number average molecular weight (Mn) of component (A) is preferably 5000 or less, more preferably 4000 or less, still more preferably 3500 or less or 3000 or less. The lower limit of the Mn is not particularly limited and can be, for example, 200 or more, 300 or more, 400 or more, etc. The Mn of component (A) can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0083] (B) component, the solvent, is not particularly limited as long as it is one or more solvents selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans. When the reaction solvent is not removed or only a part of it is removed during the production of the polyester resin, component (B) may be solvent A used as the reaction solvent. Therefore, in one embodiment, the resin crosslinking agent of the present invention contains the polyester resin obtained by the production method of the present invention and solvent A used as the reaction solvent. Alternatively, when the reaction solvent is removed during the production of the polyester resin, one or more solvents selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans may be added to the obtained polyester resin. Component (B) is as described in the [Method for Producing Polyester Resin] section above, including its preferred examples.

[0084] In the resin crosslinking agent of the present invention, the amount ratio of component (A) to component (B) can be arbitrarily determined as long as component (A) can be dissolved in component (B). In the resin crosslinking agent of the present invention, even when component (A) is a rigid backbone type active ester resin having an aromatic polycyclic skeleton, it can be in a sufficiently dissolved state, and thus has the advantage that the resin composition described below can be easily prepared.

[0085] [Resin Composition] A resin composition can be produced using the polyester resin obtained by the production method of the present invention. The present invention also provides such a resin composition. For example, the resin composition of the present invention may contain a crosslinkable resin and a polyester resin, and is characterized in that the polyester resin is the polyester resin obtained by the production method of the present invention.

[0086] In one embodiment, the resin composition of the present invention contains (A) a polyester resin, (B) one or more solvents selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans, and (C) a crosslinkable resin.

[0087] The polyester resin as the component (A) is as described in the above [Production Method of Polyester Resin] column, including acid halide compounds and aromatic hydroxy compounds as raw materials. Also, the preferred range of its number average molecular weight (Mn) is as described in the above [Resin Crosslinking Agent] column.

[0088] The solvent as the component (B) is not particularly limited as long as it is one or more solvents selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans. When the reaction solvent is not removed or only a part of it is removed during the production of the polyester resin, the component (B) may be the solvent A used as the reaction solvent. Therefore, in one embodiment, the resin composition of the present invention contains the polyester resin obtained by the production method of the present invention, the solvent A used as the reaction solvent, and a crosslinkable resin. Alternatively, when the reaction solvent is completely removed during the production of the polyester resin, one or more solvents selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans may be added to the obtained polyester resin together with the crosslinkable resin. The component (B) is as described in the above [Production Method of Polyester Resin] column, including its preferred examples.

[0089] As the crosslinkable resin which is the component (C), the type thereof is not particularly limited as long as it can crosslink in combination with the component (A). From the viewpoint of being able to provide a cured product having excellent dielectric properties in combination with the component (A), the component (C) is preferably at least one selected from the group consisting of a thermosetting resin and a radical polymerizable resin.

[0090] As the thermosetting resin and the radical polymerizable resin, known resins used when forming an insulating layer of a printed wiring board or a semiconductor chip package may be used. Hereinafter, the thermosetting resin and the radical polymerizable resin that can be used as the component (C) will be described.

[0091] Examples of the thermosetting resin include epoxy resin, benzocyclobutene resin, epoxy acrylate resin, urethane acrylate resin, urethane resin, cyanate resin, polyimide resin, benzoxazine resin, unsaturated polyester resin, phenol resin, melamine resin, silicone resin, phenoxy resin and the like. The thermosetting resin may be used alone or in combination of two or more. Among them, from the viewpoint of being able to provide a cured product having excellent dielectric properties in combination with the component (A), the component (C) preferably contains an epoxy resin.

[0092] The type of the epoxy resin is not particularly limited as long as it has one or more (preferably two or more) epoxy groups in one molecule. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene skeleton type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy resin, and the like.

[0093] The epoxy resin can be classified into a liquid epoxy resin (hereinafter referred to as "liquid epoxy resin") at a temperature of 20°C and a solid epoxy resin (hereinafter referred to as "solid epoxy resin") at a temperature of 20°C. However, the resin composition of the present invention may contain only the liquid epoxy resin, only the solid epoxy resin, or a combination of the liquid epoxy resin and the solid epoxy resin as the component (C). When containing a combination of the liquid epoxy resin and the solid epoxy resin, the blending ratio (liquid:solid) may be in the range of 20:1 to 1:20 by mass ratio (preferably 10:1 to 1:10, more preferably 3:1 to 1:3).

[0094] The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 2000 g / eq., more preferably 60 g / eq. to 1000 g / eq., and still more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the epoxy resin containing one equivalent of epoxy groups and can be measured according to JIS K7236.

[0095] The weight average molecular weight (Mw) of the epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, and even more preferably from 400 to 1,500. The Mw of the epoxy resin can be measured as a polystyrene-equivalent value by the GPC method.

[0096] The radical polymerizable resin is not particularly limited as long as it has one or more (preferably two or more) radical polymerizable unsaturated groups in one molecule. Examples of the radical polymerizable resin include resins having one or more selected from maleimide groups, vinyl groups, allyl groups, styryl groups, vinylphenyl groups, acryloyl groups, methacryloyl groups, fumaroyl groups, and maleoyl groups as the radical polymerizable unsaturated groups. Among them, from the viewpoint of being able to provide a cured product having excellent dielectric properties in combination with the component (A), the component (C) preferably contains one or more selected from maleimide resins, (meth)acrylic resins, and styryl resins.

[0097] The maleimide resin is not particularly limited as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule. Examples of the maleimide resin include maleimide resins containing an aliphatic skeleton having 36 carbon atoms derived from dimer diamine such as "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", "BMI-689" (all manufactured by DIC Corporation); maleimide resins containing an indane skeleton described in the Invention Association Public Technical Report Public Technical Number 2020-500211; maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group such as "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Daiwa Kasei Co., Ltd.), and "BMI-80" (manufactured by KAI Chemical Co., Ltd.).

[0098] (Meta)acrylic resins are not particularly limited in type as long as they have one or more (preferably two or more) (meta)acryloyl groups in one molecule. Here, the term "(meta)acryloyl group" is a general term for acryloyl group and methacryloyl group. Examples of methacrylic resins include "(meta)acrylic resins" such as "A-DOG" (manufactured by Shin-Nakamura Chemical Co., Ltd.), "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA" (all manufactured by Nippon Kayaku Co., Ltd.).

[0099] Styryl resins are not particularly limited in type as long as they have one or more (preferably two or more) styryl groups or vinylphenyl groups in one molecule. Examples of styryl resins include styryl resins such as "OPE-2St", "OPE-2St 1200", "OPE-2St 2200" (all manufactured by Mitsubishi Gas Chemical Company, Inc.).

[0100] The resin composition of the present invention may contain only a thermosetting resin as the component (C), may contain only a radically polymerizable resin, or may contain a combination of a thermosetting resin and a radically polymerizable resin.

[0101] In the resin composition of the present invention, the mass ratio of the component (A) to the component (C) ((A) / (C)) is not particularly limited as long as the component (C) can be crosslinked, but is preferably 0.2 or more, more preferably 0.4 or more, 0.5 or more, 0.6 or more, 0.8 or more, 1 or more. The upper limit of the mass ratio ((A) / (C)) may be, for example, 2 or less, 1.9 or less, 1.8 or less, etc. Therefore, in one embodiment, the mass ratio of the component (A) to the component (C) ((A) / (C)) is 0.2 to 2.0.

[0102] The resin composition of the present invention may further contain an inorganic filler. By containing an inorganic filler, the linear thermal expansion coefficient and the dielectric tangent can be further reduced.

[0103] Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, etc., and it may be selected according to the specific use. The inorganic filler may be used alone or in combination of two or more. Examples of commercially available inorganic fillers include "UFP-30" (manufactured by Denka Chemical Industry Co., Ltd.); "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SC4050-SX", "SO-C4", "SO-C2", "SO-C1", "SC-C2" (all manufactured by Admatechs Co., Ltd.); "Silfill NSS-3N", "Silfill NSS-4N", "Silfill NSS-5N" (manufactured by Tokuyama Corporation), "DAW-0525" (manufactured by Denka Co., Ltd.), etc.

[0104] The average particle size of the inorganic filler may be determined within a suitable range according to the specific application. For example, when forming an interlayer insulating layer of a printed wiring board or a redistribution layer of a semiconductor chip package, from the viewpoint of achieving a low roughness on the surface of the cured product (insulating layer) and facilitating the formation of fine wiring, the average particle size of the inorganic filler is preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less. When forming a sealing layer of a semiconductor chip package, from the viewpoint of improving the fluidity during the sealing molding, the average particle size of the inorganic filler is preferably 15 μm or less, more preferably 14 μm or less, even more preferably 12 μm or less, 10 μm or less, or 8 μm or less. The lower limit of the average particle size is not particularly limited and may be determined according to the specific application, and can be, for example, 0.01 μm or more, 0.02 μm or more, 0.03 μm or more, 0.05 μm or more, or 0.1 μm or more. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a volume-based particle size distribution of the inorganic filler using a laser diffraction / scattering particle size distribution measuring device and taking the median diameter as the average particle size. As the measurement sample, a dispersion of the inorganic filler in water by ultrasonic waves can preferably be used. As the laser diffraction / scattering particle size distribution measuring device, LA-950 manufactured by Horiba, Ltd. etc. can be used.

[0105] The inorganic filler is preferably one whose moisture resistance and dispersibility are improved by surface treatment with a surface treatment agent such as an aminosilane coupling agent, a ureidoxysilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a vinylsilane coupling agent, a styrylsilane coupling agent, an acrylate silane coupling agent, an isocyanate silane coupling agent, a sulfide silane coupling agent, an organosilazane compound, or a titanate coupling agent.

[0106] When the resin composition of the present invention contains an inorganic filler, the content of the inorganic filler in the resin composition may be determined according to the properties required for the resin composition. However, when the non-volatile components in the resin composition are taken as 100% by mass, for example, it is 5% by mass or more, 10% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more, 75% by mass or more, or 80% by mass or more. The upper limit of the content of the inorganic filler in the resin composition is not particularly limited, but can be, for example, 95% by mass or less, 90% by mass or less, etc.

[0107] The resin composition of the present invention may further contain a resin crosslinking agent other than the polyester resin.

[0108] Examples of the resin crosslinking agent other than the polyester resin include phenolic curing agents such as "TD2090", "TD2131" (manufactured by DIC Corporation), "MEH-7600", "MEH-7851", "MEH-8000H" (manufactured by Meiwa Kasei Co., Ltd.), "NHN", "CBN", "GPH-65", "GPH-103" (manufactured by Nippon Kayaku Co., Ltd.), "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", "SN395" (manufactured by Nippon Steel Chemical & Material Co., Ltd.), "LA7052", "LA7054", "LA3018", "LA1356" (manufactured by DIC Corporation); benzoxazine-based crosslinking agents such as "F-a", "P-d" (manufactured by Shikoku Kasei Co., Ltd.), "HFB2006M" (manufactured by Showa Highpolymer Co., Ltd.); acid anhydride-based crosslinking agents such as methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride; cyanate ester-based crosslinking agents such as PT30, PT60, BA230S75 (manufactured by Lonza Japan Co., Ltd.), and the like.

[0109] When the resin composition of the present invention contains a resin crosslinking agent other than a polyester resin, the content of the resin crosslinking agent in the resin composition may be determined according to the properties required for the resin composition. However, when the non-volatile components in the resin composition are 100% by mass, it is preferably 40% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and the lower limit may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, etc.

[0110] The resin composition of the present invention may further contain a crosslinking accelerator. By containing a crosslinking accelerator, the crosslinking time and crosslinking temperature can be efficiently adjusted.

[0111] Examples of the crosslinking accelerator include organic phosphine compounds such as "TPP", "TPP-K", "TPP-S", "TPTP-S" (manufactured by Kitakyo Chemical Industry Co., Ltd.); imidazole compounds such as "Curezol 2MZ", "2E4MZ", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", "Cl1Z-A", "2MZ-OK", "2MA-OK", "2PHZ" (manufactured by Shikoku Kasei Kogyo Co., Ltd.); amine adduct compounds such as Novacure (manufactured by Asahi Kasei Corporation), Fujicure (manufactured by Fujikasei Kogyo Co., Ltd.); amine compounds such as 1,8-diazabicyclo[5,4,0]undecene-7, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 4-dimethylaminopyridine; and organometallic complexes or organometallic salts such as cobalt, copper, zinc, iron, nickel, manganese, tin, etc.

[0112] When the resin composition of the present invention contains a crosslinking accelerator, the content of the crosslinking accelerator in the resin composition may be determined according to the properties required for the resin composition. However, when the non-volatile components in the resin composition are 100% by mass, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, and the lower limit may be 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, etc.

[0113] The resin composition of the present invention may further contain optional additives. Such additives include, for example, organic fillers such as rubber particles; radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, and polyester resins; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as benton and montmorillonite; defoaming agents such as silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, and vinyl resin-based defoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic-based flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers, etc. The content of such additives may be determined according to the properties required for the resin composition.

[0114] The resin composition of the present invention may further contain an organic solvent other than the component (B) (hereinafter also referred to as "other organic solvent") as a volatile component. Examples of the other organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as ethylbenzene and trimethylbenzene. The other organic solvent may be used alone or in combination of two or more kinds.

[0115] The resin composition of the present invention can be prepared by appropriately mixing the necessary components among the above components, and kneading or mixing them by kneading means such as a three-roll mill, ball mill, bead mill, sand mill, etc., or stirring means such as a super mixer, planetary mixer, etc., as necessary. When the resin composition of the present invention contains the component (A) and the component (B) in combination, since the component (A) is easily soluble, it is possible to easily prepare the resin composition.

[0116] The resin composition of the present invention can be suitably used as a resin composition for sealing a semiconductor chip (resin composition for semiconductor encapsulation). The resin composition of the present invention can also be suitably used as a resin composition for a rewiring formation layer as an insulating layer for forming a rewiring layer in a semiconductor chip package (resin composition for rewiring formation layer). The resin composition of the present invention can further be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for insulating layer of printed wiring board), and more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for interlayer insulating layer of printed wiring board). The resin composition of the present invention can also be suitably used when the printed wiring board is a component-embedded circuit board. The resin composition of the present invention can further be widely used in applications where a resin composition is required, such as sheet-like laminated materials such as resin sheets and prepregs, solder resists, underfill materials, die bonding materials, hole-filling resins, component-embedding resins, etc.

[0117] [Sheet-like laminated material (resin sheet, prepreg)] The resin composition of the present invention can be used as it is, or it may be used in the form of a sheet-like laminated material containing the resin composition.

[0118] As the sheet-like laminated material, the following resin sheets and prepregs are preferred.

[0119] In one embodiment, the resin sheet includes a support and a layer of a resin composition (hereinafter simply referred to as a "resin composition layer") provided on the support, and is characterized in that the resin composition layer is formed from the resin composition of the present invention.

[0120] The thickness of the resin composition layer varies depending on the application, and may be appropriately determined depending on the application. For example, from the viewpoint of thinning printed wiring boards and semiconductor chip packages, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, 120 μm or less, 100 μm or less, 80 μm or less, 60 μm or less, or 50 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 1 μm or more, 5 μm or more, etc.

[0121] Examples of the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0122] When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, with inexpensive polyethylene terephthalate being particularly preferred.

[0123] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0124] The support may be subjected to matting treatment, corona treatment, or antistatic treatment on the surface that joins the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface that joins the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The support with a release layer may be a commercially available product. For example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin-based release agent, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., etc.

[0125] The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferable, and a range of 10 μm to 60 μm is more preferable. When using a support with a release layer, it is preferable that the total thickness of the support with a release layer is within the above range.

[0126] As the support, a metal foil with a support substrate, in which a support substrate that can be peeled off is laminated on a thin metal foil, may also be used. In one embodiment, the metal foil with a support substrate includes a support substrate, a release layer provided on the support substrate, and a metal foil provided on the release layer. When using a metal foil with a support substrate as the support, the resin composition layer is provided on the metal foil.

[0127] In the metal foil with a support substrate, the material of the support substrate is not particularly limited, and examples thereof include copper foil, aluminum foil, stainless steel foil, titanium foil, copper alloy foil, etc. When using a copper foil as the support substrate, it may be an electrolytic copper foil or a rolled copper foil. Further, the release layer is not particularly limited as long as the metal foil can be peeled off from the support substrate, and examples thereof include an alloy layer of elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, and P; an organic film, etc.

[0128] In the metal foil with a support substrate, as the material of the metal foil, for example, copper foil and copper alloy foil are preferable.

[0129] In the metal foil with a support substrate, the thickness of the support substrate is not particularly limited, but is preferably in the range of 10 μm to 150 μm, and more preferably in the range of 10 μm to 100 μm. Further, the thickness of the metal foil may be, for example, in the range of 0.1 μm to 10 μm.

[0130] In one embodiment, the resin sheet may further include any layer as needed. Examples of such an arbitrary layer include a protective film or the like provided on a surface of the resin composition layer that is not joined to the support (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust or the like to the surface of the resin composition layer and scratches can be suppressed.

[0131] The resin sheet can be produced, for example, by preparing a varnish-like resin composition, applying this on a support using a die coater or the like, and further drying to form a resin composition layer.

[0132] The drying may be carried out by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it also 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, the resin composition layer can be formed by drying at 50 °C to 150 °C for 3 minutes to 10 minutes. When the component (B) is included as the organic solvent, in addition to volatilizing under normal film-forming conditions, since the component (B) has high safety as described above, it is possible to produce the resin sheet while highly considering safety from the viewpoint of safety.

[0133] The resin sheet can be wound and stored in a roll shape. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0134] In one embodiment, the prepreg is formed by impregnating a sheet-shaped fiber base material with the resin composition of the present invention.

[0135] The sheet-shaped fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning printed wiring boards and semiconductor chip packages, the thickness of the sheet-shaped fiber base material is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-shaped fiber base material is not particularly limited. Usually, it is 10 μm or more.

[0136] The prepreg can be manufactured by known methods such as the hot melt method and the solvent method.

[0137] The thickness of the prepreg can be in the same range as the resin composition layer in the resin sheet described above.

[0138] The sheet-shaped laminated material of the present invention can be suitably used for sealing a semiconductor chip (for semiconductor sealing), and can be suitably used as an insulating layer for forming a redistribution layer (for redistribution layer formation). The sheet-shaped laminated material of the present invention can also be suitably used for forming an insulating layer of a printed wiring board (for insulating layer of printed wiring board), and can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for interlayer insulating layer of printed wiring board).

[0139] [Semiconductor Chip Package] The semiconductor chip package of the present invention includes a sealing layer made of a cured product of the resin composition of the present invention. The semiconductor chip package of the present invention may also include an insulating layer (redistribution layer formation layer) made of a cured product of the resin composition of the present invention for forming a redistribution layer, as described above.

[0140] The semiconductor chip package can be manufactured, for example, by a method including the following steps (1) to (6) using the resin composition and resin sheet of the present invention. In order to form the sealing layer in step (3) or the rewiring formation layer in step (5), the resin composition and resin sheet of the present invention may be used. Hereinafter, an example of forming the sealing layer and the rewiring formation layer using the resin composition and resin sheet is shown. However, the technology for forming the sealing layer and the rewiring formation layer of the semiconductor chip package is known, and those skilled in the art can manufacture the semiconductor package according to the known technology using the resin composition and resin sheet of the present invention. (1) Step of laminating a temporary fixing film on a base material (2) Step of temporarily fixing a semiconductor chip on the temporary fixing film (3) Step of forming a sealing layer on the semiconductor chip (4) Step of peeling the base material and the temporary fixing film from the semiconductor chip (5) Step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled, and (6) Step of forming a rewiring layer as a conductor layer on the rewiring formation layer

[0141] - Step (1)- The material used for the base material is not particularly limited. Examples of the base material include a silicon wafer; a glass wafer; a glass substrate; a metal substrate such as copper, titanium, stainless steel, cold-rolled steel sheet (SPCC); a substrate impregnated with an epoxy resin or the like in glass fibers and subjected to heat curing treatment (for example, an FR-4 substrate); a substrate made of a bismaleimide triazine resin (BT resin), and the like.

[0142] The material of the temporary fixing film is not particularly limited as long as it can be peeled from the semiconductor chip in step (4) and can temporarily fix the semiconductor chip. Commercially available products can be used as the temporary fixing film. Examples of commercially available products include Rivar Alpha manufactured by Nitto Denko Corporation.

[0143] - Step (2)- Temporarily fix the semiconductor chip on the temporary fixing film such that the electrode pad surface thereof is joined to the temporary fixing film. The temporary fixing of the semiconductor chip can be performed using a known apparatus such as a flip chip bonder or a die bonder. The layout and the number of arrangements of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, etc. For example, they can be aligned and temporarily fixed in a matrix form with multiple rows and multiple columns.

[0144] - Step (3)- Apply the resin composition of the present invention on the semiconductor chip, or laminate the resin composition layer of the resin sheet of the present invention on the semiconductor chip, and cure (for example, thermally cure) it to form a sealing layer.

[0145] For example, when used in the form of a resin sheet, the lamination of the semiconductor chip and the resin sheet can be performed by removing the protective film of the resin sheet and then thermocompression bonding the resin sheet to the semiconductor chip from the support side. As a member for thermocompression bonding the resin sheet to the semiconductor chip (hereinafter, also referred to as "thermocompression bonding member"), for example, a heated metal plate (such as a SUS mirror plate) or a metal roll (such as a SUS roll) can be mentioned. Note that it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface unevenness of the semiconductor chip instead of directly pressing the thermocompression bonding member against the resin sheet. The lamination of the semiconductor chip and the resin sheet may be carried out by a vacuum lamination method, and the lamination conditions are the same as the lamination conditions described later in relation to the manufacturing method of the printed wiring board, and the preferable ranges are also the same.

[0146] After lamination, thermally cure the resin composition to form a sealing layer. The conditions for thermal curing are the same as the conditions for thermal curing described later in relation to the manufacturing method of the printed wiring board.

[0147] The support of the resin sheet may be peeled off after laminating and thermally curing the resin sheet on the semiconductor chip, or the support may be peeled off before laminating the resin sheet on the semiconductor chip.

[0148] When forming a sealing layer by applying the resin composition of the present invention, the coating conditions may be the same as those for forming the resin composition layer described in relation to the resin sheet of the present invention.

[0149] - Step (4) - The method of peeling the base material and the temporary fixing film can be appropriately changed according to the material of the temporary fixing film, etc. For example, methods such as heating and foaming (or expanding) the temporary fixing film to peel it, and irradiating ultraviolet rays from the base material side to reduce the adhesive force of the temporary fixing film and peel it can be mentioned.

[0150] In the method of heating and foaming (or expanding) the temporary fixing film to peel it, the heating conditions are usually 100 to 250 °C for 1 to 90 seconds or 5 to 15 minutes. Also, in the method of irradiating ultraviolet rays from the base material side to reduce the adhesive force of the temporary fixing film and peel it, the irradiation amount of ultraviolet rays is usually 10 mJ / cm 2 ~1000 mJ / cm 2 is.

[0151] - Step (5) - The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties when forming the rewiring formation layer (insulating layer). From the viewpoint of ease of manufacturing a semiconductor chip package, a photosensitive resin and a thermosetting resin are preferable. The rewiring formation layer may be formed using the resin composition and resin sheet of the present invention.

[0152] After forming the rewiring formation layer, in order to layer-connect the semiconductor chip and the conductor layer described later, via holes may be formed in the rewiring formation layer. The via holes may be formed by a known method according to the material of the rewiring formation layer.

[0153] - Step (6) - The material of the conductor layer formed on the rewiring formation layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single-metal layer or an alloy layer. Examples of the alloy layer include layers formed from alloys of two or more metals selected from the above group (for example, nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). Among them, from the viewpoints of general applicability in forming the conductor layer, cost, ease of patterning, etc., a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy is preferable, a single-metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferable, and a single-metal layer of copper is even more preferable.

[0154] The conductor layer may have a single-layer structure or a multilayer structure in which two or more single-metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0155] The thickness of the conductor layer depends on the design of the desired semiconductor chip package, but is generally 1 μm to 35 μm, preferably 1 μm to 20 μm.

[0156] In one embodiment, the conductor layer may be formed by plating. For example, by plating on the surface of the rewiring formation layer by a conventionally known technique such as a semi-additive method or a full-additive method, a conductor layer having a desired wiring pattern can be formed. From the viewpoint of manufacturing simplicity, it is preferable to form it by the semi-additive method. Hereinafter, an example of forming the conductor layer by the semi-additive method is shown.

[0157] First, an electroless plating seed layer is formed on the surface of the rewiring formation layer by electroless plating. Next, a mask pattern is formed on the formed electroless plating seed layer to expose a part of the electroless plating seed layer corresponding to a desired wiring pattern. After forming a metal layer by electrolytic plating on the exposed electroless plating seed layer, the mask pattern is removed. Thereafter, an unnecessary electroless plating seed layer is removed by etching or the like, and a conductor layer (rewiring layer) having a desired wiring pattern can be formed.

[0158] Note that steps (5) and (6) may be repeated to alternately stack (build up) the conductor layer (rewiring layer) and the rewiring formation layer (insulating layer).

[0159] In manufacturing a semiconductor chip package, steps of (7) forming a solder resist layer on the conductor layer (rewiring layer), (8) forming bumps, and (9) dicing and singulating a plurality of semiconductor chip packages into individual semiconductor chip packages may be further performed. These steps may be carried out according to various methods known to those skilled in the art used for manufacturing semiconductor chip packages.

[0160] The above is an example of a manufacturing method in which a semiconductor chip is first provided and a rewiring layer is formed on the electrode pad surface thereof, that is, the Chip-1 st ) method. The semiconductor chip package of the present invention, in addition to such a Chip-1 method, first provides a rewiring layer, and a semiconductor chip is provided and sealed in a state where the electrode pad surface thereof can be electrically connected to the rewiring layer, that is, it may be manufactured by the Rewiring Layer-1 (RDL-1 st ) method.

[0161] By forming a sealing layer and a redistribution layer using the resin composition and resin sheet of the present invention, a semiconductor package can be realized with low transmission loss regardless of whether it is a Fan-In type package or a Fan-Out type package. In one embodiment, the semiconductor chip package of the present invention is a Fan-Out type package. The resin composition and resin sheet of the present invention can be applied regardless of whether it is a Fan-Out panel level package (FOPLP) or a Fan-Out wafer level package (FOWLP). In one embodiment, the semiconductor package of the present invention is a Fan-Out panel level package (FOPLP). In another embodiment, the semiconductor package of the present invention is a Fan-Out wafer level package (FOWLP).

[0162] [Printed Wiring Board] The printed wiring board of the present invention includes an insulating layer made of a cured product of the resin composition of the present invention.

[0163] The printed wiring board can be manufactured, for example, by a method including the following steps (I) and (II) using the above resin sheet. (I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is joined to the inner layer substrate (II) A step of curing (e.g., thermally curing) the resin composition layer to form an insulating layer

[0164] The "inner layer substrate" used in Process (I) is a member that serves as the substrate of a printed wiring board. Examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Further, the substrate may have a conductor layer on one or both sides, and this conductor layer may be pattern-processed. An inner layer substrate with a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an "inner layer circuit board". Also, in the production of a printed wiring board, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the "inner layer substrate" as defined in the present invention. When the printed wiring board is a component-built-in circuit board, an inner layer substrate incorporating components may be used.

[0165] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS mirror plate) or a metal roll (such as a SUS roll). Note that the thermocompression bonding member may be pressed directly against the resin sheet, or may be pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

[0166] The lamination of the inner layer substrate and the resin sheet may be carried out by the vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the thermocompression bonding pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination can preferably be carried out under reduced pressure conditions of a pressure of 26.7 hPa or less.

[0167] The lamination can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include the vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., the Vacuum Applicator manufactured by Nichco Materials Co., Ltd., and the batch-type vacuum pressurizing laminator.

[0168] After lamination, under normal pressure (atmospheric pressure), for example, by pressing the heat-bonding member from the support side, a smoothing process of the laminated resin sheet may be performed. The pressing conditions for the smoothing process can be the same as the heat-bonding conditions for the above lamination. The smoothing process can be performed by a commercially available laminator. Note that the lamination and the smoothing process may be continuously performed using the above-mentioned commercially available vacuum laminator.

[0169] The support may be removed between step (I) and step (II), or may be removed after step (II). Note that when a metal foil is used as the support, a conductor layer may be formed using the metal foil without peeling the support. Also, when a metal foil with a support substrate is used as the support, the support substrate (and the release layer) may be peeled off. And a conductor layer can be formed using the metal foil.

[0170] In step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer made of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and the conditions usually employed when forming an insulating layer of a printed wiring board may be used.

[0171] For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition and the like. In one embodiment, the curing temperature is preferably 120°C to 250°C, more preferably 150°C to 240°C, and even more preferably 180°C to 230°C. The curing time can be preferably 5 minutes to 240 minutes, more preferably 10 minutes to 150 minutes, and even more preferably 15 minutes to 120 minutes.

[0172] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C to 120°C, preferably 60°C to 115°C, more preferably 70°C to 110°C for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes.

[0173] When manufacturing a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art used for manufacturing printed wiring boards. When removing the support after step (II), the removal of the support may be carried out between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). Further, if necessary, the formation of the insulating layer and the conductor layer in steps (I) to (V) may be repeated to form a multilayer wiring board.

[0174] In another embodiment, the printed wiring board of the present invention can be manufactured using the above-described prepreg. The manufacturing method is basically the same as the case of using a resin sheet.

[0175] Step (III) is a step of drilling holes in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be carried out using, for example, a drill, a laser, a plasma, etc., according to the composition of the resin composition used for forming the insulating layer. The dimensions and shapes of the holes may be appropriately determined according to the design of the printed wiring board.

[0176] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), removal of smear (desmear) is also performed. The procedures and conditions for the roughening treatment are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.

[0177] The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution. Preferably, it is an alkaline solution, and as the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Security P" and "Swelling Dip Security SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited, but for example, it can be carried out by immersing the insulating layer in the swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in the swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0178] The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in the oxidizing agent solution heated to 60°C to 100°C for 10 minutes to 30 minutes. Further, the concentration of the permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan Co., Ltd.

[0179] Also, as the neutralizing liquid used for the roughening treatment, an acidic aqueous solution is preferable, and examples of commercially available products include "Reduction Solution Security P" manufactured by Atotech Japan Co., Ltd.

[0180] The treatment with the neutralizing liquid can be carried out by immersing the treated surface, which has been roughened with the oxidizing agent, in the neutralizing liquid at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with the oxidizing agent in the neutralizing liquid at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

[0181] Step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. Step (V) may be carried out in the same manner as step (6) described in relation to the method for manufacturing a semiconductor chip package.

[0182] The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally from 3 μm to 35 μm, preferably from 5 μm to 30 μm.

[0183] The conductor layer may also be formed using a metal foil. When forming the conductor layer using a metal foil, it is preferable to carry out step (V) between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be carried out by a vacuum lamination method. The lamination conditions may be the same as those described for step (I). Next, step (II) is carried out to form the insulating layer. Thereafter, using the metal foil on the insulating layer, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method.

[0184] The metal foil can be manufactured by a known method such as an electrolytic method or a rolling method. Examples of commercially available metal foils include HLP foil, JXUT-III foil manufactured by JX Nippon Mining & Metals Corporation, 3EC-III foil, TP-III foil manufactured by Mitsui Mining & Smelting Co., Ltd., and the like.

[0185] Alternatively, as described above, when a metal foil or a metal foil with a support substrate is used as the support of the resin sheet, the conductor layer may be formed using the metal foil.

[0186] [Semiconductor device] The semiconductor device of the present invention includes a layer made of a cured product of the resin composition of the present invention. The semiconductor device of the present invention can be manufactured using the semiconductor chip package or printed wiring board of the present invention.

[0187] Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trains, ships, and aircraft).

Example

[0188] Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "mass%" respectively unless otherwise specified.

[0189] <Example 1> Production of Polyester Resin (1) Into a 0.5-liter four-necked round flask equipped with a stirrer, thermometer, dropping funnel, and nitrogen gas inlet, 33 g of a dicyclopentadiene-phenol adduct (J-DPP85 manufactured by JFE Chemical Co., Ltd., hydroxyl equivalent 165 g / eq.) as an aromatic hydroxy compound, 14.4 g of 1-naphthol, 30.5 g of isophthaloyl chloride as a halide compound, 0.39 g of an interlayer transfer catalyst, and 130 g of cyclopentyl methyl ether as a reaction solvent were charged (chloride group: aromatic hydroxy group = 0.3 mol: 0.3 mol), and stirred while blowing nitrogen gas to completely dissolve. 60.0 g of a 20% aqueous NaOH solution was added dropwise at 30°C over 1 hour while paying attention to heat generation so that the temperature was finally raised to 60°C. Then, after further stirring at 60°C for 2 hours, 50 g of distilled water was added to completely dissolve the by-produced inorganic salts, and then the solution was transferred to a separatory funnel and allowed to stand for liquid separation to discard the lower layer (aqueous layer). After repeating washing with water 3 times to completely neutralize, dehydration was performed by azeotropic distillation and precision filtration. The solution was vacuum distilled at 200°C to remove the solvent, thereby obtaining 56 g of the target polyester resin (1).

[0190] <Examples 2 to 8> Production of Polyester Resins (2) to (8) Except for changing the reaction solvent, acid halide compound, and aromatic hydroxy compound to the types shown in Table 1 below, polyester resins (2) to (8) were produced in the same manner as in Example 1. The acid halide compound and the aromatic hydroxy compound were used in amounts such that the halide group: aromatic hydroxy group = 0.3 mol: 0.3 mol (the aromatic hydroxy group was 0.1 mol derived from a monovalent aromatic hydroxy compound and 0.2 mol derived from a divalent aromatic hydroxy compound), and the addition amount of the reaction solvent was about 167% by mass based on 100% by mass of the total amount of the acid halide compound and the aromatic hydroxy compound.

[0191] <Comparative Examples 1 to 4> Production of Polyester Resins (C1) to (C4) Except for changing the reaction solvent, acid halide compound, and aromatic hydroxy compound to the types shown in Table 2 below, polyester resins (C1) to (C4) were produced in the same manner as in Example 1. The acid halide compound and the aromatic hydroxy compound were used in amounts such that the halide group: aromatic hydroxy group = 0.3 mol: 0.3 mol (the aromatic hydroxy group was 0.1 mol derived from a monovalent aromatic hydroxy compound and 0.2 mol derived from a divalent aromatic hydroxy compound), and the addition amount of the reaction solvent was about 167% by mass based on 100% by mass of the total amount of the acid halide compound and the aromatic hydroxy compound.

[0192] In the examples and comparative examples, the oil-water separability after the condensation reaction (when standing and separating in the separatory funnel) was evaluated according to the following criteria.

[0193] Evaluation Criteria for Oil-Water Separability: ○: The organic layer and the aqueous layer are clearly separated. △: The organic layer or the aqueous layer is turbid and it takes time to separate. ×: The whole becomes an emulsion state and separation is difficult.

[0194]

Table 1

[0195]

Table 2

[0196] For the polyester resins (1) to (8), 22 parts of the polyester resin, 27 parts of an epoxy resin ("NC3000" manufactured by Nippon Kayaku Co., Ltd.), 74 parts of an inorganic filler ("SC4050-SX" manufactured by Admatechs Co., Ltd.), and 0.6 parts of a crosslinking accelerator (4-dimethylaminopyridine (DMAP)) were dissolved in 45 parts of a solvent to prepare a varnish-like resin composition. The solvent used was cyclopentyl methyl ether, cyclohexyl methyl ether, or 4-methyltetrahydropyran.

[0197] The obtained resin composition was applied to a support (polyethylene terephthalate film, thickness 38 μm) using a die coater so that the thickness of the resin composition layer after drying would be 40 μm, and then dried at 120° C. for 2 minutes to produce a resin sheet. This enabled the production of a resin sheet having a resin composition layer with good coatability and uniform thickness.

Claims

1. In the condensation reaction of an acid halide compound and an aromatic hydroxy compound, a method for producing a polyester resin, wherein at least one solvent A selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans is used as a reaction solvent.

2. The method for producing a polyester resin according to claim 1, wherein the polyester resin contains an active ester group.

3. The method for producing a polyester resin according to claim 1 or 2, wherein the acid halide compound is divalent and the aromatic hydroxy compound is a mixture of monovalent and divalent.

4. The method for producing a polyester resin according to claim 1 or 2, wherein the acid halide compound is a mixture of monovalent and divalent and the aromatic hydroxy compound is divalent.

5. The method for producing a polyester resin according to any one of claims 1 to 4, wherein the molar ratio of the halide group to the aromatic hydroxy group is in the range of the former: the latter = 1.00: 0.80 to 1.00: 1.

20.

6. The method for producing a polyester resin according to any one of claims 1 to 5, wherein the polyester resin contains an average of 2 to 10 active ester groups per molecule.

7. The method for producing a polyester resin according to any one of claims 1 to 6, wherein the boiling point of the solvent A is in the range of 70 to 150 °C.

8. The method for producing a polyester resin according to any one of claims 1 to 7, wherein the cycloalkyl alkyl ether is represented by the following formula (1) and the alkyl tetrahydropyran is represented by the following formula (2). 【Chemical 1】 (In the formula, R11 represents a cycloalkyl group having 3 to 10 carbon atoms, R12 represents an alkyl group having 1 to 6 carbon atoms.) 【Chemical 2】 (In the formula, R21 represents an alkyl group having 1 to 6 carbon atoms.)

9. The method for producing a polyester resin according to any one of claims 1 to 8, wherein the solvent A contains cyclopentyl methyl ether, cyclohexyl methyl ether or 4-methyltetrahydropyran.

10. The method for producing a polyester resin according to any one of claims 1 to 9, wherein the addition amount of the solvent A is 30 to 500% by mass based on 100% by mass of the total amount of the acid halide compound and the aromatic hydroxy compound.

11. The following steps (1) to (4): (1) A step of dissolving an acid halide compound and an aromatic hydroxy compound in at least one solvent A selected from the group consisting of cycloalkyl alkyl ethers and alkyl tetrahydropyrans to obtain a solution; Step (2): adding a dehydrohalogenating agent to the solution to perform a condensation reaction; Step (3): after the condensation reaction, adding water and performing oil-water separation to discharge the by-produced salt out of the system; and Step (4): further performing washing with water and oil-water separation to purify The method for producing a polyester resin according to any one of claims 1 to 10, comprising the above steps.

12. The following steps (5) and (6): Step (5): performing a dehydration treatment to precipitate the by-produced salt; and Step (6): removing the by-produced salt by filtration The method for producing a polyester resin according to claim 11, further comprising the above steps.

13. A resin crosslinking agent containing a polyester resin obtained by the production method according to any one of claims 1 to 12 and solvent A used as a reaction solvent.

14. A resin composition containing a polyester resin obtained by the production method according to any one of claims 1 to 12 and solvent A used as a reaction solvent, and a crosslinkable resin.

15. The resin composition according to claim 14, further containing an inorganic filler.

16. The resin composition according to any one of claims 14 and 15, which is used for an insulating layer of a printed wiring board.

17. The resin composition according to any one of claims 14 and 15, which is used for semiconductor encapsulation.

18. A sheet-like laminated material containing the resin composition according to any one of claims 14 to 17.

19. A printed wiring board including an insulating layer made of a cured product of the resin composition according to any one of claims 14 to 16.

20. A semiconductor chip package including a sealing layer made of a cured product of the resin composition according to any one of claims 14 to 15 and 17.

21. The semiconductor chip package according to claim 20, which is a fan-out type package.

22. A semiconductor device including the printed wiring board according to claim 19 or the semiconductor chip package according to claim 20 or 21.

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