Curable resin, cured product thereof, resin composition, and production method for curable resin

Abstract

The present invention provides a curable resin containing a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3) (in formula (1), R1 is a divalent group having one or more of at least one among an ethylenic double bond and an acetylenic triple bond, and in formula (2), R2 is a divalent group having an alicyclic structure).

Description

Curable resin, cured product thereof, resin composition, and method for producing curable resin

[0001] The present invention relates to a curable resin, a cured product thereof, a resin composition, a method for producing the curable resin, and the like.

[0002] Polyester carbonates are used in a variety of applications due to their excellent mechanical strength, heat resistance, transparency, etc., and various polyester carbonates and methods for producing them have been reported.

[0003] For example, Patent Document 1 discloses a polyester carbonate polyol having a norbornane skeleton.

[0004] Patent Document 2 discloses a polyester carbonate resin having a 1,1'-binaphthalene structure and a fluorene structure, and according to Patent Document 2, such a resin is said to exhibit excellent optical performance.

[0005] Patent Document 3 discloses a method for producing a polyester carbonate resin by reacting a reactant containing a dihydroxy compound having a fluorene structure. According to Patent Document 3, this method for producing such a resin is capable of producing a resin having excellent fluidity and / or tensile strength.

[0006] Japanese Patent Application Laid-Open No. 05-105746 International Publication No. 2015 / 170691 International Publication No. 2017 / 078074

[0007] As described above, various polyester carbonates are known, but these polyester carbonates have low compatibility with curable resins and are difficult to add to curable resins. Furthermore, there is still room for improvement in the properties of the conventional polyester carbonates. Therefore, an object of the present invention is to provide curable resins and the like that have excellent dielectric properties.

[0008] As a result of extensive research, the present inventors have found that a curable resin containing a predetermined structural unit has excellent dielectric properties, and have thus completed the present invention.

[0009] The present invention includes the following embodiments: [1] A curable resin including a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3). (In the above formula (1), R １ is a divalent group having at least one ethylenic double bond and at least one acetylenic triple bond, and in the above formula (2), R ２ is a divalent group having an alicyclic structure.) [2] The curable resin according to [1], wherein the molar ratio of the sum of the contents of the structural unit represented by formula (1), the structural unit represented by formula (2), and the structural unit represented by formula (3) to all structural units constituting the curable resin is 0.60 or more and 1.0 or less. [3] The curable resin according to [1] or [2], wherein the structural unit represented by formula (3) is derived from at least one selected from the group consisting of dialkyl carbonate, diaryl carbonate, and alkylaryl carbonate. [4] The curable resin according to any one of [1] to [3], wherein the structural unit represented by formula (1) is derived from at least one selected from the group consisting of fumaric acid, maleic acid, and maleic anhydride. [5] The curable resin according to any one of [1] to [4], wherein the structural unit represented by formula (2) is derived from a dihydroxy compound containing at least one selected from the group consisting of a norbornane skeleton and a cyclohexane skeleton. [6] The curable resin according to any one of [1] to [5], wherein the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) is 0.010 or more and less than 1.0. [7] The curable resin according to any one of [1] to [6], wherein the molar ratio of the structural unit represented by formula (3) to the structural unit represented by formula (2) is 0.10 or more and 1.5 or less. [8] The number average molecular weight is 5.00 × 10 ２ Above 3.00 x 10 ４The curable resin according to any one of [1] to [7], which is as follows: [9] The curable resin according to any one of [1] to [8], which contains a polyester moiety containing a structural unit represented by formula (1) and a structural unit represented by formula (2), but not containing a structural unit represented by formula (3).

[10] The curable resin according to any one of [1] to [9], which has a dielectric loss tangent of 0.010 or less, calculated according to a measurement method including the following steps (i) to (iii): (i) A cured product of a resin composition containing the curable resin is prepared, and the dielectric loss tangent at 10 GHz of the cured product is measured. (ii) A measurement similar to that in step (i) is performed on multiple cured products in which the contents of each component of the resin composition are changed. (iii) The measurement results of steps (i) and (ii) are extrapolated to calculate the dielectric loss tangent of the curable resin alone.

[11] A cured product of the curable resin according to any one of [1] to

[10] .

[12] A resin composition comprising the curable resin according to any one of [1] to

[10] .

[13] The resin composition according to

[12] , wherein the content of the curable resin is 1.0 part by mass or more per 100 parts by mass of the resin component.

[14] A method for producing a curable resin, comprising reacting at least one of a compound represented by the following formula (4) and a compound represented by the following formula (4'), with a compound represented by the following formula (5), and a compound represented by the following formula (6). (In the above formula (4), R １ is a divalent group having at least one ethylenic double bond and at least one acetylenic triple bond, and R ３ and R ４ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms, and in the above formula (4'), R １ is R in the above formula (4) １ In the above formula (5), R ２ is a divalent group having an alicyclic structure, and R ５ and R ６ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms, and in the above formula (6), R ７ and R ８are each independently any substituent.)

[15] The production method according to

[14] , comprising: a step of reacting the compound represented by formula (5) with at least one of the compound represented by formula (4) and the compound represented by formula (4') below, in a molar equivalent amount less than that of the compound represented by formula (5); and a step of reacting the product obtained by the above step with the compound represented by formula (6).

[16] The resin composition according to

[12] or

[13] , which is used for an electronic material.

[17] An electronic component comprising a cured product of the resin composition according to

[12] or

[13] .

[18] A fiber-reinforced composite material comprising the resin composition according to

[12] or

[13] and reinforcing fibers.

[19] A fiber-reinforced molded product which is a cured product of the fiber-reinforced composite material according to

[18] .

[20] A semiconductor encapsulation material comprising the resin composition according to

[12] or

[13] and an inorganic filler.

[21] A semiconductor device comprising a cured product of the semiconductor encapsulation material according to

[20] .

[22] A prepreg comprising a substrate and the resin composition according to

[12] or

[13] impregnated into or coated on the substrate.

[23] A laminate comprising the prepreg according to

[22] .

[24] A circuit board comprising the laminate according to

[23] and a metal foil disposed on one or both sides of the laminate.

[25] A build-up film comprising a cured product of the resin composition according to

[12] or

[13] and a substrate film.

[0010] According to the present invention, it is possible to provide a curable resin or the like having excellent dielectric properties.

[0011] Hereinafter, an embodiment for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail, but the present invention is not limited to this and various modifications are possible within the scope of the gist thereof. In this specification, a bond cut by a wavy line in a chemical structural formula means a bonding site in a structural unit represented by each chemical structural formula to another structural unit.

[0012] [Curable Resin] The curable resin of the present embodiment comprises a structural unit represented by the following formula (1) (hereinafter also referred to as a "dicarboxylic acid unit"), A structural unit represented by the following formula (2) (hereinafter also referred to as a "dihydroxy unit"), A structural unit represented by the following formula (3) (hereinafter also referred to as a "carbonate unit"), In the above formula (1), R １ is a divalent group having at least one ethylenic double bond and at least one acetylenic triple bond, and in the above formula (2), R ２ is a divalent group having an alicyclic structure.

[0013] The curable resin of this embodiment has at least one ethylenic double bond and at least one acetylenic triple bond in the dicarboxylic acid unit, and therefore can be crosslinked intramolecularly or intermolecularly, i.e., can be cured by an appropriate method. Conventional polyester carbonates do not have a site (functional group) that can crosslink with a curable resin, so when added to a curable resin with low compatibility, problems such as phase separation or peeling at the interface with the curable resin occur. Furthermore, the curable resin of this embodiment is a resin containing an ester bond and a carbonate bond, but has at least one ethylenic double bond and at least one acetylenic triple bond. Therefore, when mixed with another curable resin, it can react with the functional group of the other curable resin to crosslink. As a result, the curable resin of this embodiment can be cured alone, and even when mixed with another curable resin, phase separation and interfacial peeling are unlikely to occur.

[0014] Furthermore, it is presumed that the curable resin of this embodiment achieves a low dielectric constant and dielectric loss tangent and exhibits excellent dielectric properties due to the dihydroxy unit having an alicyclic structure, which is presumed to be due to the large molar volume of the dihydroxy unit and the restriction of the molecular chain motion of the resin molecules by the alicyclic structure, but the reasons for this are not limited to these.

[0015] In this specification, "excellent dielectric properties" means that both the dielectric constant and the dielectric dissipation factor are low. Specific values ​​of the dielectric constant and the dielectric dissipation factor are not particularly limited, but for example, when the dielectric constant (relative permittivity) of the cured product of the curable resin or resin composition prepared as in the examples is 2.7 or less and the dielectric dissipation factor is 0.010 or less, it can be said that the dielectric properties are excellent. The curable resin and resin composition of this embodiment have low dielectric constant and dielectric dissipation factor even when cured.

[0016] The dielectric constant and dielectric loss tangent of the curable resin alone of this embodiment, calculated according to the measurement methods including the following (i) to (iii), are preferably 2.7 or less and 0.010 or less, respectively. (i) A cured product of a resin composition containing the curable resin is prepared, and the dielectric loss tangent of the cured product at 10 GHz is measured. (ii) Measurements similar to (i) are carried out on multiple cured products in which the content of each component of the resin composition is changed. (iii) The measurement results of (i) and (ii) are extrapolated to calculate the dielectric loss tangent of the curable resin alone.

[0017] The resin composition in (i) is not particularly limited, but may contain, for example, an organic solvent such as toluene, a (meth)acrylate such as tricyclodecanol acrylate, and an initiator such as an organic peroxide initiator, as in Example 7 described below. The cured product may be produced as follows: The resin composition is placed in a vacuum dryer and dried at room temperature for 48 hours and at 60°C for 3 hours to remove the solvent. After the solvent is removed, the resin composition is placed in a 1 mm thick mold, sandwiched between Aflex film (manufactured by AGC Corporation) and a SUS plate, and placed in a vacuum press heated to 200°C. －２ After reducing the pressure to 100 kPa, the pressure is gradually increased to 0.6 MPa, and the mold is heated for 90 minutes before being removed and slowly cooled. After slowly cooling, the cured resin composition is removed from the mold. The removed cured product is cut into 0.8 mm wide rod-shaped samples. The cut samples are dried in a vacuum dryer at 70°C for one day.

[0018] In (ii), for example, when the resin composition in (i) contains an organic solvent such as toluene, a (meth)acrylate such as tricyclodecanol acrylate, and an initiator such as an organic peroxide initiator, as in Example 7 described below, a total of at least four samples may be cured to produce a cured product: a sample in which the amount of initiator added is increased compared to the resin composition in (i), a sample in which the amount of initiator added is decreased, and a sample in which the compounding ratio of (meth)acrylate to curable resin is increased and a sample in which the compounding ratio is decreased.

[0019] In (iii), a proportional expression between the content of each component, the dielectric constant, and the dielectric loss tangent may be calculated based on the measurement results of (i) and (ii), and extrapolation may be performed based on the proportional expression.

[0020] The dielectric constant of the curable resin alone of this embodiment, calculated according to the above measurement method, is more preferably 2.6 or less, even more preferably 2.5 or less, and even more preferably 2.4 or less. The lower limit of the dielectric constant is not particularly limited and may be, for example, 1.5, 1.8, or 2.0. The dielectric loss tangent of the curable resin alone of this embodiment, calculated according to the above measurement method, is more preferably 0.008 or less, even more preferably 0.006 or less, and even more preferably 0.005 or less. The lower limit of the dielectric loss tangent is not particularly limited and may be, for example, 0.0005, 0.0003, or 0.0001.

[0021] The dielectric constant and dielectric loss tangent of a cured product of a resin composition containing the curable resin of this embodiment and prepared in the same manner as in Example 7 described later are preferably 2.7 or less and 0.010 or less, respectively, as measured in the same manner as in Example 7 described later.

[0022] The curable resin of this embodiment is a resin that cures in response to an appropriate stimulus or spontaneously. In one aspect, the curable resin of this embodiment is a thermosetting resin, in another aspect, a photocurable resin, or in yet another aspect, a heat- or photocurable resin.

[0023] R in the dicarboxylic acid unit １is a divalent group having at least one ethylenic double bond and one or more acetylenic triple bonds. In this specification, an "ethylenic double bond" means a carbon-carbon double bond that does not form an aromatic ring. Furthermore, an "acetylenic triple bond" means a carbon-carbon triple bond. Since the curable resin of this embodiment has such a carbon-carbon unsaturated bond that does not form an aromatic ring, it can be crosslinked alone or with a crosslinking agent.

[0024] The above R １ The number of carbon atoms in R is not particularly limited, but is, for example, 2 or more and 8 or less, preferably 2 or more and 6 or less, more preferably 2 or more and 4 or less, and even more preferably 2 or more and 3 or less. １ The total number of ethylenic double bonds and acetylenic triple bonds in R is not particularly limited as long as it is 1 or more, but is, for example, 1 or more and 3 or less, preferably 1 or more and 2 or less, and more preferably 1. １ Preferably, R has an ethylenic double bond. １ A preferred embodiment of the formula (I) is, for example, a divalent hydrocarbon group having one ethylenic double bond and having from 2 to 4 carbon atoms. In this preferred embodiment, the number of ethylenic double bonds and the number of carbon atoms may be optionally changed within the above ranges.

[0025] When the dicarboxylic acid unit has an ethylenic double bond, the isomer structure is not particularly limited. That is, the dicarboxylic acid unit having an ethylenic double bond may be in a cis configuration or a trans configuration.

[0026] The dicarboxylic acid unit represented by the above formula (1) is preferably a structural unit represented by the following formula (1-1) or (1-2). Here, in the above formulas (1-1) and (1-2), R １Ａ are each independently a hydrogen atom, a methyl group, or an ethyl group. １Ａ are preferably each independently a hydrogen atom or a methyl group.

[0027] The dicarboxylic acid unit is particularly preferably a structural unit derived from fumaric acid, maleic acid, or maleic anhydride. In this case, R １ is a divalent hydrocarbon group having 2 carbon atoms and an ethylenic double bond. According to such an embodiment, the dielectric properties of the curable resin tend to be more excellent.

[0028] The curable resin of the present embodiment may contain only one type of dicarboxylic acid unit, or may contain two or more types of dicarboxylic acid units. From the viewpoint of ease of production and ease of control of the resin properties, it is preferable that the curable resin contains only one type of dicarboxylic acid unit.

[0029] R in the dihydroxy unit ２ is a divalent group having an alicyclic structure. ２ It is presumed that the main chain of the curable resin of this embodiment becomes rigid and the molar volume increases because R is a divalent group having an alicyclic structure. This presumed restricts the movement of the molecular chain of the entire resin molecule, improving the dielectric properties. However, the reason for this is not limited to this. ２ In the formula (R), the alicyclic structure may be in the main chain, in the side chain, or in both the main chain and the side chain. ２ Preferably, R has an alicyclic structure in the main chain. ２ has at least one alicyclic structure, but may have two or more alicyclic structures.

[0030] The above R ２ The number of carbon atoms in R is not particularly limited, but is, for example, 5 or more and 100 or less, preferably 6 or more and 20 or less, more preferably 7 or more and 18 or less, and even more preferably 8 or more and 17 or less. ２ The number of carbon atoms in R may be 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, or 30 or less within the above range. ２The ratio of the number of carbon atoms constituting the alicyclic structure to the number of carbon atoms contained in is not particularly limited, and is, for example, 50% or more and 100% or less. Within the above range, this ratio is preferably 60% or more, more preferably 70% or more, and even more preferably 75% or more. According to this embodiment, the movement of the molecular chain in the dihydroxy unit is further restricted, and the dielectric properties of the curable resin tend to be further improved. The upper limit of this ratio is not particularly limited, and may be, for example, 100%, 95%, 90%, or 85%. ２ may be a divalent saturated hydrocarbon group or a divalent unsaturated hydrocarbon group.

[0031] The dihydroxy unit is preferably a structural unit derived from a dihydroxy compound containing at least one selected from the group consisting of a cycloalkane skeleton and a norbornane skeleton, more preferably a structural unit derived from a dihydroxy compound containing at least one selected from the group consisting of a cyclohexane skeleton and a norbornane skeleton, still more preferably a structural unit derived from a dihydroxy compound containing at least one selected from the group consisting of a cycloalkane skeleton and a norbornane skeleton, and even more preferably a structural unit derived from a dihydroxy compound containing at least one selected from the group consisting of a cyclohexane skeleton and a norbornane skeleton. The dihydroxy unit may be a structural unit derived from a dihydroxy compound containing a norbornane skeleton, or may be a structural unit derived from a dihydroxy compound containing a norbornane skeleton. According to this embodiment, the dielectric properties of the curable resin tend to be further improved. In this specification, the term "norbornane skeleton" refers to a skeleton selected from the group consisting of a skeleton containing norbornane (bicyclo[2.2.1]heptane) and a skeleton in which a single bond in the skeleton is replaced with an unsaturated bond. Therefore, the norbornane skeleton includes, for example, a norbornane skeleton and a norbornene skeleton. The term "cycloalkane-based skeleton" refers to a skeleton selected from the group consisting of skeletons containing cycloalkane and skeletons in which a single bond in the skeleton is replaced with an unsaturated bond. Examples of cycloalkane-based skeletons include cycloalkane skeletons and cycloalkene skeletons. The term "cyclohexane-based skeleton" refers to a skeleton selected from the group consisting of skeletons containing cyclohexane and skeletons in which a single bond in the skeleton is replaced with an unsaturated bond. Examples of cyclohexane-based skeletons include cyclohexane skeletons and cyclohexene skeletons.

[0032] The dihydroxy unit represented by the formula (2) is preferably a structural unit represented by the following formula (2-4), and more preferably a structural unit represented by the following formula (2-1), (2-2), or (2-3). ２Ａ and / or R ２Ｂ and / or R ２Ｃ and / or R ２ＤThe structural unit may be a structural unit containing a structure in which the following is repeated regularly or randomly. In the above formula, R ２Ａ are each independently a single bond, a methylene group, or an ethylene group, and R ２Ｂ is a divalent alicyclic structure having 5 to 30, 5 to 20, or 5 to 15 carbon atoms, which may have an alkyl group; R ２Ｃ are each independently a single bond, a methylene group which may have at least one of a methyl group and an ethyl group, or an ethylene group, and R ２Ｄ are each independently a divalent aryl group, and R ２Ｘ are each independently R ２Ａ , R ２Ｂ , R ２Ｃ , or R ２Ｄ where n is an integer of 1 to 6. In formula (2-4), n R ２Ｘ At least one of ２Ｂ In the above formula, R ２Ａ are preferably each independently a single bond or a methylene group.

[0033] In the above formula, R ２Ｂ R may be a monocyclo ring, bicyclo ring, tricyclo ring, or polycyclo ring, which may have an alkyl group. ２Ｂ R preferably contains a cycloalkane skeleton or a norbornane skeleton, more preferably contains a cyclohexane skeleton or a norbornane skeleton, even more preferably contains a cyclohexane ring or a norbornane skeleton, still more preferably contains a cyclohexane ring or a norbornane skeleton, and particularly preferably contains a cyclohexane ring or a decahydro-1,4:5,8-dimethanonaphthalene skeleton represented by the following formula (7): ２Ｂ contains a cycloalkane skeleton, a cyclohexane skeleton, a cyclohexane ring, a norbornane skeleton, a norbornane skeleton and / or a decahydro-1,4:5,8-dimethanonaphthalene skeleton, R ２Ｂ The group bonded to may be bonded to any part of the backbone or ring, or may be bonded to another cyclo ring further bonded to the backbone.

[0034] R ２Ｂ The alkyl group that R may have is not particularly limited, but is preferably a methyl group or an ethyl group. ２Ｂ may be a divalent alicyclic structure having no alkyl group. ２Ｂ The alicyclic structure may have 0 to 6, 0 to 4, 0 to 3, 0 to 2, or 0 to 1 alkyl groups.

[0035] In the above formula, R ２Ｃ Examples of the methylene group or ethylene group which may have at least one of a methyl group and an ethyl group include a methylene group, an ethylene group, a methylmethylene group, an ethylmethylene group, a methylethylene group, an ethylethylene group, a methylethylmethylene group, a dimethylmethylene group, a diethylmethylene group, a methylethylethylene group, a dimethylethylene group, a diethylethylene group, a methyldiethylethylene group, a dimethylethylethylene group, a trimethylethylene group, a triethylethylene group, and a tetramethylethylene group, preferably a methylene group, an ethylene group, a methylmethylene group, an ethylmethylene group, a methylethylene group, an ethylethylene group, a methylethylmethylene group, a dimethylmethylene group, a diethylmethylene group, a methylethylethylene group, a dimethylethylene group, and a diethylethylene group, more preferably a methylene group, an ethylene group, a methylmethylene group, an ethylmethylene group, a methylethylene group, an ethylethylene group, a methylethylmethylene group, a dimethylmethylene group, and a diethylethylene group.

[0036] In the above formula, R ２Ｄ is preferably a benzene ring or a naphthalene ring which may have an alkyl group, and more preferably a benzene ring which may have an alkyl group. ２Ｄ The alkyl group that R may have is not particularly limited, but is preferably a methyl group or an ethyl group. ２Ｄ may be a divalent aromatic ring having no alkyl group. ２ＤThe aromatic ring may have 0 to 6, 0 to 4, 0 to 3, 0 to 2, or 0 to 1 alkyl groups.

[0037] In the above formula, (R ２Ｘ ) ｎ is a divalent group, R ２Ａ , R ２Ｂ , R ２Ｃ , and R ２Ｄ R independently selected from ２Ｘ (R ２Ｘ ) ｎ In R ２Ａ , R ２Ｂ , R ２Ｃ , and R ２Ｄ The preferred embodiments of (R ２Ｘ ) ｎ Although not particularly limited, examples of the structure include the following: ２Ｂ - -R ２Ｂ -R ２Ｃ - -R ２Ｂ -R ２Ｄ - -R ２Ｄ -R ２Ｂ -R ２Ｄ - -R ２Ｂ -R ２Ａ -R ２Ｂ - -R ２Ｂ -R ２Ｃ -R ２Ｂ - -R ２Ｂ -R ２Ｄ -R ２Ｂ - (R ２Ｘ ) ｎ R included in ２Ｂ The number may be 1 or more and 4 or less, preferably 1 or more and 3 or less, and more preferably 1 or 2. n is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, and even more preferably 1 or more and 3 or less.

[0038] The dihydroxy unit represented by the above formula (2) may be a unit derived from a dihydroxy compound having an alkylene group having from 3 to 20 carbon atoms as a main chain, and a group having an alicyclic structure bonded to a side chain of the alkylene group. The alicyclic structure in the group bonded to the side chain may be, for example, a monocyclic ring, a bicyclic ring, a tricyclic ring, or a polycyclic ring. The group bonded to the side chain may be a cycloalkyl group such as a cyclohexyl group or a monovalent group derived from a norbornane skeleton. In this embodiment, the number of carbon atoms in the dihydroxy unit may be from 5 to 100.

[0039] The dihydroxy unit may be decahydro-1,4:5,8-dimethanonaphthalene-dimethanol (D-NDM), tricyclodecane dimethanol (for example, tricyclo[5.2.1.0] represented by the formula (10) described later), or the like. ２，６ ]decane dimethanol) (TCDDM), cyclohexane dimethanol, pentacyclopentadecanedimethanol (for example, pentacyclo[6.5.1.1] represented by formula (12) described later) ３，６ .0 ２，７ .0 ９，１３

[0033] At least one selected from the group consisting of structural units derived from (pentadecanedimethanol) (PCDDM), hydrogenated bisphenol A, and (trimethylcyclohexylidene)bisphenol (TMC) is particularly preferred. In the above compounds, the bonding position of the group bonding to the alicyclic structure is not particularly limited. For example, in D-NDM, the bonding positions of the hydroxymethyl groups to the alicyclic structure are not particularly limited, and may be, for example, the 2- and 6-positions, or the 2- and 7-positions. In cyclohexanedimethanol, the bonding positions of the hydroxymethyl groups to the cyclohexane ring are not particularly limited, and may be, for example, the ortho-, meta-, or para-positions. In TMC, the bonding positions of the three methyl groups and two phenol groups to the cyclohexane ring are not particularly limited, and for example, TMC may be (3,3,5-trimethylcyclohexylidene)bisphenol, or may be 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol represented by formula (14) described below.

[0040] The curable resin of this embodiment may contain only one type of dihydroxy unit or may contain two or more types of dihydroxy units, and each dihydroxy unit may be composed of only one type of stereoisomer or may contain multiple stereoisomers.

[0041] The carbonate unit is preferably a structural unit derived from at least one selected from the group consisting of dialkyl carbonate, diaryl carbonate, and alkylaryl carbonate. Specific examples of dialkyl carbonate, diaryl carbonate, and alkylaryl carbonate will be described later.

[0042] The curable resin of this embodiment may contain additional structural units in addition to the dicarboxylic acid unit, dihydroxy unit, and carbonate unit described above. The additional structural units are not particularly limited, but are preferably those that do not adversely affect the dielectric properties of the curable resin. Examples of the additional structural units include structural units derived from dicarboxylic acid compounds other than those represented by formula (1), structural units derived from dihydroxy compounds other than those represented by formula (2), and monohydroxy compounds having an ethylenic double bond.

[0043] Such dicarboxylic acid compounds are not particularly limited, but include, for example, saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and acid anhydrides thereof. Examples of saturated aliphatic dicarboxylic acids include cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, adipic acid, succinic acid, sebacic acid, alkylsuccinic acid, cyclohexanediacetic acid, azelaic acid, malonic acid, dimethylmalonic acid, and oxalic acid. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 2,5-furandicarboxylic acid, and 2,5-thiophenedicarboxylic acid.

[0044] The dihydroxy compound is not particularly limited, but examples thereof include aliphatic dihydroxy compounds and aromatic dihydroxy compounds. Examples of the aliphatic dihydroxy compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,4-butenediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 2-ethyl-2-methylpropane-1,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,4-dimethyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol.

[0045] Examples of aromatic dihydroxy compounds include hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, xylylene glycol, 4,4'-dihydroxydiphenylbenzophenone, and bisphenols. Bisphenols include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3-phenyl)phenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, and 1,1-bis(4-hydroxyphenyl)-2-ethylhexane. , 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxy-3-nitrophenyl)methane, 3,3-bis(4-hydroxyphenyl)pentane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, bis(4-hydroxyphenyl)disulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, and 4,4'-(propane-2,2-diyl)bis(2-allylphenol).

[0046] Further, examples of aromatic dihydroxy compounds include dihydroxy compounds having an ether group bonded to an aromatic group, such as 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane, 1,3-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, and bis(4-(2-hydroxyethoxy)phenyl)sulfone; and 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy) ... butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-( Also included are dihydroxy compounds having a fluorene ring, such as 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene, and 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene.

[0047] Examples of monohydroxy compounds having an ethylenic double bond include hydroxy group-containing (meth)acrylic acid esters, and specific examples thereof include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylate.

[0048] The curable resin may also contain, as a partial structure, a structure derived from a silicone oil having a hydroxy group in the molecular structure, a structure derived from a silicone oil having a carboxy group in the molecular structure, or the like.

[0049] As the silicone oil having a hydroxy group in its molecular structure, commercially available products can be used, for example, "KF-6001" (functional group equivalent weight 900) and "KF-6002" (functional group equivalent weight 1600) having hydroxy groups at both ends, "X-22-1821" (functional group equivalent weight 1470) having phenolic hydroxy groups at both ends (all manufactured by Shin-Etsu Chemical Co., Ltd.), "BY-16-752A" (functional group equivalent weight 1500) (all manufactured by Toray Dow Corning Co., Ltd.), "X-22-170BX" (functional group equivalent weight 2800), "X-22-170DX" (functional group equivalent weight 4670), and "X-22-176DX" (functional group equivalent weight 1600) having a hydroxy group at one end. ), "X-22-176F" (functional group equivalent weight 6300) (all manufactured by Shin-Etsu Chemical Co., Ltd.), "X-22-4039" (functional group equivalent weight 970) and "X-22-4015" (functional group equivalent weight 1870) having hydroxyl groups in the side chain (all manufactured by Shin-Etsu Chemical Co., Ltd.), "SF8427" (functional group equivalent weight 930, manufactured by Dow Corning Toray Co., Ltd.) and "X-22-4952" (functional group equivalent weight 1100, manufactured by Shin-Etsu Chemical Co., Ltd.) having hydroxyl groups in the polyether at both ends; "FZ-2162" (functional group equivalent weight 750) and "SH3773M" (functional group equivalent weight 800) having hydroxyl groups in the polyether at the side chain (all manufactured by Dow Corning Toray Co., Ltd.), and the like.

[0050] Furthermore, commercially available products can be used as silicone oils having a carboxy group in their molecular structure, and examples include "X-22-162C" (functional group equivalent: 2300) having a carboxy group at both ends, "X-22-3710" (functional group equivalent: 1450) having a carboxy group at one end, and "X-22-3701E" (functional group equivalent: 4000) having a carboxy group in the side chain (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0051] By introducing the structural units and / or partial structures as described above into the curable resin of the present embodiment, properties such as flexibility, mechanical strength, heat resistance, flame retardancy, color tone, and solvent solubility tend to be improved or imparted.

[0052] The terminal groups in the curable resin of this embodiment are not particularly limited and may be, for example, carboxy groups and / or hydroxy groups, but preferably have a structure in which the carboxy groups and / or hydroxy groups are blocked with a terminal blocking agent. According to an embodiment in which a terminal blocking agent is included, the dielectric properties of the curable resin tend to be more excellent. The terminal carboxy group blocking agent is not particularly limited as long as it is a compound having a group reactive with a carboxy group, but examples thereof include carbodiimide compounds such as monocarbodiimide and polycarbodiimide compounds, oxazoline compounds, and one-terminal diols. Examples of terminal hydroxy group blocking agents include diphenyl carbonate and monocarboxylic acids.

[0053] The curable resin of this embodiment contains a dicarboxylic acid unit, a dihydroxy unit, and a carbonate unit. The order of bonding of these units is not particularly limited, but it is preferable that the dicarboxylic acid unit and the carbonate unit are adjacent to the dihydroxy unit. Here, in the curable resin, the oxygen atoms at both ends of these units are shared with the adjacent units. That is, for example, when a dihydroxy unit and a dicarboxylic acid unit are adjacent to each other, the structure forms the following ester bond. Also, when a dihydroxy unit and a carbonate unit are adjacent, the structure forms the following carbonate bond:

[0054] The curable resin of this embodiment may be a random copolymer of dicarboxylic acid units, dihydroxy units, and carbonate units, a copolymer of carbonate units and dihydroxy units linked to dicarboxylic acid units, or a copolymer of dicarboxylic acid units and dihydroxy units linked to carbonate units.

[0055] In one aspect, the curable resin of this embodiment includes a polyester moiety that contains dihydroxy units and dicarboxylic acid units but does not contain carbonate units. In this aspect, the curable resin is preferably a polyester carbonate in which multiple polyester moieties, each consisting of dihydroxy units and dicarboxylic acid units, are linked to multiple carbonate units. This aspect tends to further improve the dielectric properties of the curable resin.

[0056] Dihydroxy unit content N ＯＨ Dicarboxylic acid unit content N ＣＯＯＨ Molar ratio N ＣＯＯＨ / N ＯＨ is preferably 0.010 or more and less than 1.0, more preferably 0.025 or more and 0.50 or less, even more preferably 0.050 or more and 0.30 or less, and even more preferably 0.075 or more and 0.20 or less. ＣＯＯＨ / N ＯＨ When the molar ratio N is within the above range, the dielectric properties tend to be further improved. ＣＯＯＨ / N ＯＨ can be measured by a nuclear magnetic resonance (NMR) spectrometer.

[0057] Dihydroxy unit content N ＯＨ The content of carbonate units N ＯＣＯＯ Molar ratio N ＯＣＯＯ / N ＯＨ is preferably 0.10 or more and 1.5 or less, more preferably 0.50 or more and 1.3 or less, even more preferably 0.80 or more and 1.1 or less, and even more preferably 0.85 or more and 1.05 or less. ＯＣＯＯ / N ＯＨ When the molar ratio N is within the above range, the dielectric properties tend to be further improved. ＯＣＯＯ / N ＯＨ can be measured by a nuclear magnetic resonance (NMR) spectrometer.

[0058] All structural units N constituting the curable resin of this embodiment ａｌｌ The molar ratio of the sum of the contents of dihydroxy units, dicarboxylic acid units and carbonate units to ＯＨ +N ＣＯＯＨ+N ＯＣＯＯ ) / N ａｌｌ is preferably 0.60 or more, more preferably 0.70 or more, even more preferably 0.80 or more, and even more preferably 0.90 or more. ＯＨ +N ＣＯＯＨ +N ＯＣＯＯ ) / N ａｌｌ The upper limit of the molar ratio (N ＯＨ +N ＣＯＯＨ +N ＯＣＯＯ ) / N ａｌｌ When the molar ratio (N ＯＨ +N ＣＯＯＨ +N ＯＣＯＯ ) / N ａｌｌ can be measured by a nuclear magnetic resonance (NMR) spectrometer.

[0059] From the viewpoint of further improving the dielectric properties, solvent solubility, bleed-out resistance, etc. of the curable resin, the proportion of the structural unit represented by formula (1) among all structural units derived from the dicarboxylic acid compound in the curable resin is preferably 0.60 or more, more preferably 0.70 or more, even more preferably 0.80 or more, and even more preferably 0.90 or more. The upper limit of this proportion is not particularly limited, but may be, for example, 1.0, 0.98, or 0.96. From the same viewpoint, the proportion of the structural unit represented by formula (2) among all structural units derived from the dihydroxy compound in the curable resin is preferably 0.60 or more, more preferably 0.70 or more, even more preferably 0.80 or more, and even more preferably 0.90 or more. The upper limit of this proportion is not particularly limited, but may be, for example, 1.0, 0.98, or 0.96. The proportion of the structural unit represented by formula (1) and the proportion of the structural unit represented by formula (2) can be measured by nuclear magnetic resonance (NMR) spectroscopy.

[0060] The content of the structural units derived from each monomer can be controlled by adjusting the amount (used amount) of each monomer charged in the production of the curable resin. In this case, it is preferable to use a monomer that is easily evaporated and easily leaks out of the system in larger amounts than a monomer that is less likely to evaporate, taking into account the risk of leakage out of the system.

[0061] The number average molecular weight of the curable resin of the present embodiment is not particularly limited, but is preferably 5.00×10 ２ Above 3.00 x 10 ４ More preferably, it is 1.00 × 10 ３ Above 2.00 x 10 ４ More preferably, it is 1.50 × 10 ３ Above 1.50 x 10 ４ or less, and even more preferably 3.00 x 10 ３ Above 1.00 x 10 ４ The number average molecular weight is 3.00 × 10 or less. ４ When the number average molecular weight is 3.00×10 or less, the solubility of the curable resin in the solvent tends to be further improved. ４ The following embodiments are suitable for use in applications such as impregnating a filler (e.g., glass cloth) in a copper-clad laminate or the like, or for use in applications such as dissolving in a solvent, like unsaturated polyester. ４ When the number average molecular weight of the curable resin is 5.00×10 or less, it tends to be possible to more reliably prevent bleed-out (a phenomenon in which the resin does not react uniformly and the same composition gathers at a visible level) even when the resin is mixed with other curable resins such as maleimide resins and cured. ２ When the number average molecular weight is 100 or more, the dihydroxy units tend to be sufficiently incorporated into the resin, and the dielectric properties tend to be further improved. The number average molecular weight can be measured by gel permeation chromatography (GPC).

[0062] The curable resin of this embodiment encompasses all aspects of the curable resin obtained by arbitrarily combining all of the above-described aspects.

[0063] The curable resin of the present embodiment can be produced by reacting the compound containing the dicarboxylic acid unit, the compound containing the dihydroxy unit, and the compound containing the carbonate unit.

[0064] [Method for Producing Curable Resin] One embodiment of the present invention relates to a method for producing a curable resin. The method for producing a curable resin of this embodiment includes: a) reacting a compound represented by the following formula (4) (hereinafter also referred to as a "dicarboxylic acid compound") with at least one of a compound represented by the following formula (4') (hereinafter also referred to as a "dicarboxylic acid anhydride"), A compound represented by the following formula (5) (hereinafter also referred to as a "dihydroxy compound"), A compound represented by the following formula (6) (hereinafter also referred to as a "carbonate compound"), In the above formula (4), R １ is a divalent group having at least one ethylenic double bond and at least one acetylenic triple bond, and R ３ and R ４ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms, and in the above formula (4'), R １ is R in formula (4) １ In the above formula (5), R ２ is a divalent group having an alicyclic structure, and R ５ and R ６ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms, and in the above formula (6), R ７ and R ８ are each independently an optional substituent.

[0065] In the method for producing a curable resin of this embodiment, a dicarboxylic acid compound or a dicarboxylic acid anhydride is reacted and incorporated into the resin, thereby generating a dicarboxylic acid unit of the curable resin of this embodiment. Similarly, a dihydroxy compound and a carbonate compound are reacted and incorporated into the resin, thereby generating a dihydroxy unit and a carbonate unit of the curable resin of this embodiment, respectively. That is, the dicarboxylic acid unit, dihydroxy unit, and carbonate unit of the curable resin of this embodiment are structural units derived from the above-mentioned dicarboxylic acid compound or dicarboxylic acid anhydride, dihydroxy compound, and carbonate compound, respectively.

[0066] R in the above formulas (4) and (4′) １ , and R in the above formula (5) ２ are R in the above formula (1), １ and R in the above formula (2) ２ The preferred embodiments are also as described above.

[0067] R in dicarboxylic acid compounds and dihydroxy compounds ３ , R ４ , R ５ , and R ６ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms. When a dicarboxylic acid compound or a dihydroxy compound reacts and is incorporated into a resin, the R ３ , R ４ , R ５ , and R ６ R corresponding to ３ -OH, R ４ -OH, R ５ —OH, and R ６ The reaction proceeds by eliminating —OH. ３ , R ４ , R ５ , and R ６ is preferably a group that provides high stability to the hydroxylated compound. ３ , R ４ , R ５ , and R ６ is preferably a group with little steric hindrance.

[0068] The above R ３ , R ４ , R ５ , and R ６ are each independently preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a phenyl group, or a benzyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, even more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0069] In a preferred embodiment of the method for producing a curable resin of this embodiment, a dicarboxylic acid anhydride is used, and R ５ and R ６ In another preferred embodiment of the method for producing a curable resin of the present embodiment, a dihydroxy compound in which R ３ and R ４ is a hydrogen atom, or R ５ and R ６ is a hydrogen atom. According to such an embodiment, the curable resin tends to be produced efficiently.

[0070] In the carbonate compound, R ７ and R ８ When the carbonate compound reacts and is incorporated into the resin, the R ７ and R ８ R corresponding to ７ -OH and R ８ The reaction proceeds by eliminating —OH. ７ and R ８ is preferably a group that provides high stability to the hydroxylated compound. ７ and R ８ is preferably selected so that the carbonate compound is a stable compound.

[0071] The above R ７ and R ８is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, even more preferably an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 carbon atoms (phenyl group), and even more preferably a phenyl group.

[0072] The carbonate compound is not particularly limited, but examples thereof include diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dicyclohexyl carbonate, etc. The carbonate compound is preferably diphenyl carbonate and / or alkyl group-substituted diphenyl carbonate.

[0073] The above dicarboxylic acid compounds, dicarboxylic anhydrides, dihydroxy compounds, and carbonate compounds may be used alone or in combination of two or more.

[0074] In the method for producing the curable resin of this embodiment, a monomer or oligomer or polymer other than the dicarboxylic acid compound represented by formula (4), the dicarboxylic acid anhydride represented by formula (4'), the dihydroxy compound represented by formula (5), and the carbonate compound represented by formula (6) may be added to the reaction system and incorporated into the curable resin. Such compounds include dicarboxylic acid compounds other than the dicarboxylic acid compound represented by formula (4) and their anhydrides, dihydroxy compounds other than the dihydroxy compound represented by formula (5), monohydroxy compounds having an ethylenic double bond, silicone oils having a hydroxy group in their molecular structure, silicone oils having a carboxy group in their molecular structure, etc. Examples of these compounds include those described in detail in the description of the curable resin of this embodiment, and may be used alone or in combination of two or more.

[0075] The amounts of the dicarboxylic acid compound, dicarboxylic anhydride, dihydroxy compound, and carbonate compound used are determined based on the molar ratio N ＣＯＯＨ / N ＯＨ and N ＯＣＯＯ / N ＯＨ is preferably adjusted so as to fall within the above-mentioned preferred range. That is, the total amount of the dicarboxylic acid compound and the dicarboxylic acid anhydride used relative to the amount of the dihydroxy compound used is, in molar ratio, preferably 0.010 or more and less than 1.0, more preferably 0.025 or more and 0.50 or less, even more preferably 0.050 or more and 0.30 or less, and even more preferably 0.075 or more and 0.20 or less. The amount of the carbonate compound used relative to the amount of the dihydroxy compound used is, in molar ratio, preferably 0.10 or more and 1.5 or less, more preferably 0.50 or more and 1.3 or less, even more preferably 0.80 or more and 1.1 or less, and even more preferably 0.85 or more and 1.05 or less. Note that, with regard to the amount of each compound used, the ease of evaporation of each compound (for example, saturated vapor pressure at the reaction temperature) may be used as an index, and the amount of the compound used that is more easily evaporated may be increased.

[0076] In the method for producing a curable resin of this embodiment, the molar ratio of the sum of the amounts of dicarboxylic acid compound, dicarboxylic anhydride, dihydroxy compound, and carbonate compound used in the total amount of compounds used is preferably 0.60 or more, more preferably 0.70 or more, even more preferably 0.80 or more, and even more preferably 0.90 or more. The upper limit of this ratio is not particularly limited, but may be, for example, 1.0, 0.98, or 0.96. By setting the ratio to 0.60 or more, it tends to be possible to produce a curable resin that is even more excellent in dielectric properties, solvent solubility, bleed-out resistance, etc.

[0077] From the viewpoint of obtaining a curable resin having even more excellent dielectric properties, solvent solubility, bleed-out resistance, etc., the ratio of the amount of the dicarboxylic acid compound and dicarboxylic acid anhydride represented by formula (4) or (4') used among all compounds having two carboxy groups and their anhydrides used in the production method of this embodiment is preferably 0.60 or more, more preferably 0.70 or more, even more preferably 0.80 or more, and even more preferably 0.90 or more. The upper limit of this ratio is not particularly limited, but may be, for example, 1.0, 0.98, or 0.96. From the same viewpoint, the ratio of the amount of the dihydroxy compound represented by formula (5) used among all compounds having two hydroxy groups used in the production method of this embodiment is preferably 0.60 or more, more preferably 0.70 or more, even more preferably 0.80 or more, and even more preferably 0.90 or more. The upper limit of this ratio is not particularly limited, but may be, for example, 1.0, 0.98, or 0.96.

[0078] In one aspect, the method for producing a curable resin of this embodiment may include Step 1A, in which at least one of a dicarboxylic acid compound and a dicarboxylic acid anhydride is reacted with a dihydroxy compound, and Step 1B, in which the product obtained in Step 1A is reacted with a carbonate compound. In Step 1A, the total amount of the dicarboxylic acid compound and the dicarboxylic acid anhydride used is preferably less than the amount of the dihydroxy compound used, in molar terms. According to this aspect, a polyol compound is produced in Step 1A, and tends to react favorably with the carbonate compound in Step 1B. In Step 1B, the amount of the carbonate compound used, in molar terms, is preferably greater than the number of moles obtained by subtracting the total amount of the dicarboxylic acid compound and the dicarboxylic acid anhydride used from the amount of the dihydroxy compound used. According to this aspect, since a larger amount of carbonate compound is used than the number of hydroxy groups in the product obtained in Step 1A, the amount of terminal hydroxy groups in the resulting curable resin can be reduced. This tends to result in a curable resin with better dielectric properties.

[0079] In another aspect, the method for producing a curable resin of this embodiment may include step 2A of reacting a carbonate compound with a dihydroxy compound, and step 2B of reacting the product obtained in step 2A with at least one of a dicarboxylic acid compound and a dicarboxylic acid anhydride. In step 2A, the amount of the carbonate compound used is preferably less than the amount of the dihydroxy compound used, in molar terms. According to this aspect, a polyol compound is produced in step 2A, and tends to react favorably with the dicarboxylic acid compound and / or dicarboxylic acid anhydride in step 2B. In step 2B, the total amount of the dicarboxylic acid compound and dicarboxylic acid anhydride used is preferably approximately the same as the number of moles obtained by subtracting the amount of the carbonate compound used from the amount of the dihydroxy compound used, in molar terms. According to this aspect, since a dicarboxylic acid compound and / or dicarboxylic acid anhydride having a number of hydroxy groups similar to that of the product obtained in step 2A is used, the reaction completion rate in step 2B tends to be favorable.

[0080] The reactions in Step 1A and Step 2B may be carried out by heating the reactants at normal pressure. The reactions in Step 1A and Step 2B may be carried out by heating the reactants at normal pressure and then further heating under reduced pressure. The reaction temperature in Step 1A and Step 2B is not particularly limited as long as it is a temperature-elevating condition, but is, for example, 80 to 290°C (both limits included; the same applies in this specification unless otherwise specified), preferably 120 to 270°C, and more preferably 150 to 250°C. When the reactions in Step 1A and Step 2B are carried out under reduced pressure, the pressure in the system is not particularly limited as long as it is a reduced pressure condition, but is, for example, 100 kPa or less, preferably 50 kPa or less, more preferably 30 kPa or less, and even more preferably 15 kPa or less.

[0081] The reactions in steps 1B and 2A may be carried out by heating the reactants at normal pressure. The reactions in steps 1B and 2A may also be carried out by heating the reactants at normal pressure and then further heating under reduced pressure. The reactions in steps 1B and 2A may also be carried out by gradually increasing the temperature and reducing the pressure, and finally maintaining the temperature and pressure under increased pressure. The reaction temperature (final temperature) in steps 1B and 2A is not particularly limited as long as the reaction is carried out under temperature-elevating conditions, but is, for example, 100 to 290°C, preferably 130 to 280°C, and more preferably 160 to 260°C. When the reactions in steps 1B and 2A are carried out under reduced pressure, the pressure in the system is not particularly limited as long as the reaction is carried out under reduced pressure conditions, but is, for example, 10 kPa or less, preferably 5 kPa or less, and more preferably 1 kPa or less.

[0082] Steps 1A, 1B, 2A, and 2B are preferably carried out in the presence of an inert gas, such as nitrogen gas or argon gas.

[0083] In each of Steps 1A, 1B, 2A, and 2B, if a reactant is solid, it may be supplied as a solid, or may be supplied in a molten state by heating, or may be supplied as an aqueous solution, and if a reactant is liquid, it may be supplied as a single liquid or as a mixture with a solvent. The reaction may be carried out in a batch system, a continuous system, or a combination of a batch system and a continuous system.

[0084] Steps 1A, 1B, 2A, and 2B are preferably carried out in the presence of a catalyst. Examples of the catalyst include catalysts commonly used in the synthesis of polycarbonates and polyesters. Specific examples include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and salts of titanium, tin, zinc, zirconium, and / or lead. It is also possible to use a basic compound, such as a basic boron compound or a basic phosphorus compound, in combination with the alkali metal compound and / or alkaline earth metal compound.

[0085] Examples of the alkali metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. Specific examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenylborohydride, and boron phenylide. Examples of the phenylboronate include potassium, lithium phenylboron, cesium phenylboron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, alcoholates and phenolates of sodium, potassium, lithium and cesium, and disodium salt, dipotassium salt, dilithium salt and dicesium salt of bisphenol A.

[0086] Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds. Specific examples include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.

[0087] Examples of the nitrogen-containing compound include quaternary ammonium hydroxides and their salts, amines, etc. Specific examples include quaternary ammonium hydroxides having an alkyl group and / or an aryl group, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines, such as triethylamine, dimethylbenzylamine, and triphenylamine; secondary amines, such as diethylamine and dibutylamine; primary amines, such as propylamine and butylamine; imidazoles, such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole; and bases or basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0088] Examples of titanium salts include tetramethyl titanate, tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetraisobutyl titanate, and tetraphenyl titanate. Examples of tin salts include tin(II) chloride, tin(IV) chloride, tin(II) acetate, tin(IV) acetate, dibutyltin oxide, dibutyltin dilaurate, dibutyltin dimethoxide, and dibutyltin diacetate. Examples of zinc salts include zinc acetate, zinc benzoate, and zinc 2-ethylhexanoate. Examples of zirconium salts include zirconium acetylacetonate, zirconium oxyacetate, and zirconium tetrabutoxide. Examples of lead salts include lead(II) acetate and lead(IV) acetate.

[0089] In addition, examples of basic boron compounds that can be used in combination with alkali metal compounds and / or alkaline earth metal compounds include sodium salts, potassium salts, lithium salts, calcium salts, barium salts, magnesium salts, and strontium salts of tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl boron, tributylphenyl boron, tetraphenyl boron, benzyltriphenyl boron, methyltriphenyl boron, and butyltriphenyl boron, etc.

[0090] Examples of basic phosphorus compounds include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

[0091] Other catalysts commonly used in the synthesis of polycarbonates and polyesters include antimony compounds such as diantimony trioxide; germanium compounds such as germanium dioxide and germanium tetroxide; manganese compounds; and catalysts disclosed in U.S. Pat. Nos. 4,025,492, 4,136,089, 4,176,224, 4,238,593, and 4,208,527, as well as R.E. Wilfong, Journal of Polymer Science, 54, 385, (1961), and the like.

[0092] The above catalysts may be used alone or in combination of two or more. In the production method of this embodiment, a titanium salt catalyst is preferably used. In an embodiment using a catalyst, it is sufficient to add the catalyst in steps 1A and 2A, and it is not necessarily necessary to add a new catalyst in steps 1B and 2B. Alternatively, the reaction may be carried out under a catalyst in only some of the steps of the production method of this embodiment.

[0093] The amount of the catalyst used is not particularly limited, but is, for example, 0.1 to 500 μmol, preferably 0.5 to 100 μmol in terms of metal atom, per mole of all dihydroxy compounds used in the reaction.

[0094] In at least one of the above steps 1A, 1B, 2A, and 2B, the above-mentioned compounds other than the dicarboxylic acid compound represented by formula (4), the dicarboxylic acid anhydride represented by formula (4'), the dihydroxy compound represented by formula (5), and the carbonate compound represented by formula (6) may be added to the reaction system and reacted together with the dicarboxylic acid compound, the dicarboxylic acid anhydride, the dihydroxy compound, and / or the carbonate compound. The method for producing a curable resin of this embodiment may have another step other than the above steps 1A, 1B, 2A, and 2B, in which the above-mentioned compounds other than the dicarboxylic acid compound represented by formula (4), the dicarboxylic acid anhydride represented by formula (4'), the dihydroxy compound represented by formula (5), and the carbonate compound represented by formula (6) are reacted exclusively.

[0095] The method for producing a curable resin according to this embodiment may include a step of purifying the resulting product after reacting a dicarboxylic acid compound and / or a dicarboxylic acid anhydride with a dihydroxy compound and a carbonate compound as described above. This purification step may involve removing unreacted reactants and / or by-products and / or catalyst components incorporated into the curable resin. Examples of by-products include compounds produced by the condensation reaction of a dicarboxylic acid anhydride, a dihydroxy compound, and a carbonate compound. The purification step may be performed using any method commonly used to purify resins. Specifically, this may include a reprecipitation method in which the resin is dissolved in a solvent and then dropped into a poor solvent or water, or a liquid-liquid extraction method. Liquid-liquid extraction using toluene and an aqueous sodium carbonate solution is preferred for the purification step. This method tends to produce a curable resin with superior dielectric properties after purification because toluene, which has a low dielectric constant, is used as the oil phase. This purification step may also be performed between each step (e.g., between steps 1A and 2A, or between steps 1B and 2B).

[0096] Regarding the method for producing the curable resin of this embodiment, "Polyester Resin Handbook" (written by Eiichiro Takiyama, published by Nikkan Kogyo Shimbun) may be referred to as appropriate. In addition to the production method described above, the curable resin of this embodiment may also be produced by a method in which at least one of a dicarboxylic acid compound and a dicarboxylic acid anhydride is reacted with a polycarbonate diol. The polycarbonate diol used is not particularly limited as long as it contains a carbonate bond and has hydroxy groups at both ends, and examples thereof include conventionally known, commercially available polycarbonate diols. The reaction conditions and catalysts that may be used may be the same as those in step 2B described above. Furthermore, in the production method including steps 1A and 1B and the production method including steps 2A and 2B, a polycarbonate diol may be used instead of the dihydroxy compound represented by formula (5). The polycarbonate diol used is not particularly limited as long as it contains a carbonate bond and has hydroxy groups at both ends, and examples thereof include conventionally known, commercially available polycarbonate diols. According to such an embodiment, it is likely that a curable resin containing a large amount of carbonate units can be obtained.

[0097] The method for producing a curable resin according to the present embodiment encompasses all aspects of the method for producing a curable resin obtained by arbitrarily combining all of the above-described aspects.

[0098] [Resin Composition] One embodiment of the present invention relates to a resin composition containing the curable resin of this embodiment. The resin composition of this embodiment may further contain other components in addition to the curable resin of this embodiment. Examples of other components that may be contained in the resin composition of this embodiment include epoxy resins, cyanate ester compounds, maleimide compounds, BT resins, compounds having a polymerizable unsaturated group, compounds having an ester structure derived from a phenol group and an aromatic carboxylic acid group, modified silicone oils, heat stabilizers, antioxidants, curing agents, and curing accelerators. The above components may be used alone or in combination of two or more.

[0099] Examples of epoxy resins include phenol phenyl aralkyl novolac epoxy resins, phenol biphenyl aralkyl epoxy resins, naphthol aralkyl epoxy resins, anthraquinone epoxy resins, polyoxynaphthylene epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, trifunctional phenol epoxy resins, tetrafunctional phenol epoxy resins, naphthalene epoxy resins, biphenyl epoxy resins, aralkyl novolac epoxy resins, alicyclic epoxy resins, polyol epoxy resins, glycidyl amine, glycidyl ester, or butadiene double bond epoxidized compounds, compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin, and halides thereof. These may be used alone or in combination of two or more.

[0100] Examples of the cyanate ester compound include naphthol aralkyl cyanate ester compounds, novolac cyanate esters, phenol biphenyl aralkyl cyanate ester compounds, bis(3,5-dimethyl 4-cyanatophenyl)methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis(4-cyanatophenyl)ether, bis( Examples of such isocyanates include 1,4-cyclohexanediisocyanate, 1,6-hexamethylene diisocyanate, 2,2-bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, 2,2-bis(4-cyanatophenyl)propane, polymethylene polyphenyl polyisocyanate, m-tetramethylxylene diisocyanate, hydrogenated xylylene diisocyanate (1,3-bis(isocyanatomethyl)cyclohexane), isophorone diisocyanate, norbornene diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated methylene bisphenylene diisocyanate, 1,4-cyclohexane diisocyanate, 1,6-hexamethylene diisocyanate, trimethylene diisocyanate, and trifunctional isocyanates having an isocyanurate ring obtained by trimerizing a bifunctional isocyanate compound. These may be used alone or in combination of two or more.

[0101] Examples of maleimide compounds include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, prepolymers of these maleimide compounds, and prepolymers of maleimide compounds and amine compounds. These may be used alone or in combination of two or more.

[0102] BT resin is a prepolymer obtained by dissolving a cyanate ester compound and a maleimide compound in an organic solvent such as methyl ethyl ketone, N-methylpyridin, dimethylformamide, dimethylacetamide, toluene, or xylene, and then heating and mixing them. The cyanate ester compound and maleimide compound may be any of those listed above. These may be used alone or in combination of two or more.

[0103] The compound having a polymerizable unsaturated group is not particularly limited, and examples thereof include vinyl compounds such as ethylene, styrene, divinylbenzene, and divinylbiphenyl; methyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, tricyclodecanol(meth)acrylate, tricyclodecanol di(meth)acrylate, tricyclodecanol tri(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, and trimethylolpropane tri(meth)acrylate. Examples of the compound having a polymerizable unsaturated group include (meth)acrylates of monohydric or polyhydric alcohols such as bisphenol A epoxy (meth)acrylate and bisphenol F epoxy (meth)acrylate; allyl compounds such as allyl chloride, allyl acetate, allyl ether, propylene, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, and diallyl maleate; benzocyclobutene resins; and (bis)maleimide resins. These compounds having a polymerizable unsaturated group can be used alone or in combination of two or more.

[0104] Examples of compounds having an ester structure derived from a phenol group and an aromatic carboxylic acid group include a compound having one phenolic hydroxyl group (a1), a compound having two or more phenolic hydroxyl groups (a2) and an aromatic polycarboxylic acid or its acid halide (a3) ​​as a reaction raw material, an activated ester resin (I), a compound having two or more phenolic hydroxyl groups (b1), an aromatic monocarboxylic acid or its acid halide (b2) and an aromatic polycarboxylic acid or its acid halide (b3) as a reaction raw material, an activated ester resin (II) can be mentioned. Specific examples of these compounds can be found in WO 2020 / 003824. These may be used alone or in combination of two or more.

[0105] The modified silicone oil may have a chain-like siloxane skeleton and a group other than hydrogen or a hydrocarbon group in its molecular structure. Examples of the modified group include an epoxy group, an amino group, a hydroxyl group, a methacryl group, a mercapto group, a carboxyl group, an alkoxy group, and a silanol group. These may be used alone or in combination of two or more.

[0106] Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specific examples include triphenyl phosphite, tris(nonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, Examples of suitable phosphates include bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphinate, dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. These may be used alone or in combination of two or more.

[0107] Examples of antioxidants include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tri Examples of such an alkyl ester include methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis(2,4-di-tert-butylphenyl), and 3,9-bis{1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane. These may be used alone or in combination of two or more.

[0108] Examples of curing agents include polyfunctional phenolic compounds such as phenol novolac, cresol novolac, and aminotriazine novolac resin; amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone; and acid anhydrides such as phthalic anhydride, pyromellitic anhydride, and maleic anhydride. Examples of curing accelerators include organometallic salts and organometallic complexes such as zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, bis(acetylacetonate) cobalt(II), tris(acetylacetonate) cobalt(III), zinc(II) acetylacetonate, and iron(III) acetylacetonate; imidazoles and their derivatives; organic phosphorus compounds; secondary amines; tertiary amines; and quaternary ammonium salts. These may be used alone or in combination of two or more.

[0109] Among the above components, the resin composition of the present embodiment preferably contains a component that reacts with the curable resin of the present embodiment and cures together with it, such as (meth)acrylate, isocyanurate, maleimide compound, compound having a vinyl group, compound having an allyl group, etc.

[0110] The resin composition may further contain an initiator for initiating curing. Examples of the initiator include organic peroxide initiators that initiate curing by heating and ultraviolet initiators that initiate curing by light irradiation. Examples of the organic peroxide initiator include ketone peroxides such as methyl ethyl ketone peroxide and acetyl acetone peroxide; diacyl peroxides such as benzoyl peroxide; peroxy esters such as t-butyl peroxybenzoate; hydroperoxides such as cumene hydroperoxide; and dialkyl peroxides such as dicumyl peroxide. Examples of the ultraviolet initiator include benzophenones such as benzophenone, benzil, and methyl orthobenzoyl benzoate; benzoin ethers such as benzoin alkyl ethers; acetophenones such as benzil dimethyl ketal, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, and 1,1-dichloroacetophenone; and thioxanthones such as 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone.

[0111] The resin composition may further contain a crosslinking agent other than those described above. However, since the curable resin of this embodiment has an ethylenic double bond and / or an acetylenic triple bond, it can be cured alone without using a crosslinking agent. Therefore, the resin composition of this embodiment does not need to contain a crosslinking agent.

[0112] The content of the curable resin of this embodiment contained in the resin composition may be, for example, 1.0 part by mass or more relative to 100 parts by mass of the resin component (the resin and the component that cures together with the resin; synonymous with the solid component). For example, when the curable resin of this embodiment is added to the resin composition as a compatibilizer, the content of the curable resin of this embodiment may be, for example, 1.0 part by mass or more and 10 parts by mass or less, or 3.0 parts by mass or more and 5.0 parts by mass or less relative to 100 parts by mass of the resin component.

[0113] Alternatively, the content of the curable resin of this embodiment contained in the resin composition may be, for example, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, or 95 parts by mass or more, per 100 parts by mass of the resin component. When the content of the curable resin of this embodiment is within the above range, a resin composition with even better dielectric properties tends to be obtained. Furthermore, the cured product of such a resin composition tends to have a low yellowness index, i.e., a good color tone. The upper limit of the content of the curable resin of this embodiment contained in the resin composition is not particularly limited and may be 100 parts by mass, 99 parts by mass, 95 parts by mass, 90 parts by mass, or 80 parts by mass, per 100 parts by mass of the resin component. The content of components other than the curable resin of this embodiment contained in the resin composition may be appropriately adjusted as long as the content of the curable resin of this embodiment in the resin composition is within the above range.

[0114] The resin composition may further contain a reinforcing substrate or a filler such as an inorganic filler. The inorganic filler is not particularly limited as long as it is one commonly used in the art. Specific examples include silicas such as natural silica, fused silica, amorphous silica, and hollow silica; aluminum hydroxide, heat-treated aluminum hydroxide (aluminum hydroxide heated to remove some of the water of crystallization), magnesium hydroxide, and boehmite; nitride compounds such as aluminum nitride and boron nitride; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc borate, zinc stannate, alumina, clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, short glass fibers (fine glass powders such as E-glass and D-glass), hollow glass, spherical glass, titanium oxide, silicone rubber, and silicone composite powder. Examples of reinforcing substrates include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The filler may be used alone or in combination of two or more.

[0115] The content of the filler in the resin composition is not particularly limited and is, for example, 1 to 2,000 parts by mass per 100 parts by mass of the resin component. The content of the filler can be appropriately changed depending on the application of the resin composition.

[0116] The resin composition may contain a silane coupling agent or a wetting and dispersing agent in addition to the filler. By containing these components, the dispersibility of the filler, particularly the inorganic filler, tends to be improved, and further the adhesive strength between the resin and the filler tends to be improved. The silane coupling agent is not particularly limited as long as it is a silane coupling agent that is generally used for the surface treatment of inorganic materials. Specific examples include aminosilane-based silane coupling agents such as γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane; epoxysilane-based silane coupling agents such as γ-glycidoxypropyltrimethoxysilane; vinylsilane-based silane coupling agents such as γ-methacryloxypropyltrimethoxysilane; cationic silane-based silane coupling agents such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane-based silane coupling agents; and styrylsilane-based coupling agents such as p-styryltrimethoxysilane, p-styryltriethoxysilane, p-styrylmethyldimethoxysilane, p-styrylmethyldiethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride. The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used in paints. Specific examples of wetting and dispersing agents include Disperbyk-110, 111, 180, 161, BYK-W996, W9010, and W903 manufactured by BYK Japan Co., Ltd. These silane coupling agents and wetting and dispersing agents may be used alone or in combination of two or more.

[0117] Furthermore, the resin composition of this embodiment may contain a solvent as needed. When the resin composition contains an organic solvent, the viscosity during preparation of the resin composition tends to decrease, and handling properties tend to improve. The solvent is not particularly limited as long as it can dissolve at least one component in the resin composition. Specific examples include ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide; propylene glycol methyl ether and its acetate; and the like. The solvent may be used alone or in combination of two or more.

[0118] [Cured Product] One embodiment of the present invention relates to a cured product of the curable resin of the present embodiment and a cured product of the resin composition of the present embodiment. The cured product of the present embodiment is a cured product containing the curable resin of the present embodiment, and therefore has excellent dielectric properties. In addition, the cured product of the present embodiment tends to have a good color tone.

[0119] The method for curing the curable resin or resin composition of this embodiment is not particularly limited and may be appropriately selected depending on the type of resin. Examples of the curing method include thermal curing and photocuring. When curing the resin composition, it is preferable to first dissolve and mix the resin composition in a solvent, dry the mixture, and then cure the mixture so that the components are uniformly mixed.

[0120] [Applications] The curable resin, resin composition, and cured product thereof according to this embodiment can be used in, for example, electronic materials. Specific examples include electronic components, semiconductor encapsulation materials, molded resins, rigid substrates, prepregs, laminates, resin-coated copper foils, circuit boards, underfill materials, and build-up films. Other applications include fiber-reinforced composite materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, either alone or together with additives such as unsaturated polyesters and epoxy resins.

[0121] The fiber-reinforced composite material contains the resin composition of this embodiment and reinforcing fibers, and can be cured to produce a fiber-reinforced molded product. The reinforcing fibers are not particularly limited, and examples thereof include glass fibers, carbon fibers, boron fibers, and aramid fibers. The semiconductor encapsulation material contains the resin composition of this embodiment and an inorganic filler, and is used in the manufacture of semiconductor devices. The inorganic filler may be any of those described above.

[0122] The prepreg includes a substrate and a resin composition impregnated or coated on the substrate. The method for producing the prepreg can be carried out according to a conventional method and is not particularly limited. For example, the prepreg can be produced by impregnating or coating the substrate with the resin composition and then semi-curing (B-stage) it by heating it in a dryer at 100 to 200°C for 1 to 30 minutes. The substrate is not particularly limited, and known materials used in various printed wiring board materials can be appropriately selected and used depending on the intended application and performance. Specific examples of fibers constituting the substrate include, but are not limited to, glass fibers such as E-glass, D-glass, S-glass, Q-glass, spherical glass, NE-glass, L-glass, and T-glass; inorganic fibers other than glass, such as quartz; wholly aromatic polyamides such as polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.) and copolyparaphenylene-3,4'-oxydiphenylene terephthalamide (Technora (registered trademark), manufactured by Teijin Techno Products Co., Ltd.); polyesters such as 2,6-hydroxynaphthoic acid-parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.) and Zexion (registered trademark, manufactured by KB Seiren); and organic fibers such as polyparaphenylene benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.) and polyimide. These substrates may be used alone or in combination of two or more.

[0123] The laminate is a laminate containing at least a prepreg. The laminate can be obtained, for example, by laminating and molding a prepreg and another layer. The other layer is not particularly limited, but may be, for example, a separately prepared wiring board for an inner layer.

[0124] The circuit board includes a laminate and a metal foil disposed on one or both sides of the laminate. The circuit board is, for example, a copper foil-clad laminate obtained by laminating the prepreg and copper foil and curing the laminate. The copper foil used is not particularly limited as long as it is used for circuit boards, but known copper foils such as rolled copper foil and electrolytic copper foil are preferred.

[0125] The build-up film includes a cured product of a resin composition and a substrate film. "Build-up" refers to the production of a multilayer printed wiring board by laminating prepregs or resin sheets and repeatedly performing processes such as drilling and wiring on each layer.

[0126] Further effects of this embodiment are expected to include, for example, low thermal expansion, crack prevention, good color tone, solvent solubility, and suppression of separation of resins during curing.

[0127] The present invention will be described in more detail below using examples and comparative examples, but the technical scope of the present invention is not limited to these.

[0128] [Measurement of number average molecular weight of curable resin] The curable resin was dissolved in tetrahydrofuran so that the resin concentration was 0.2% by mass, and measured by gel permeation chromatography (GPC). The number average molecular weight of each curable resin was calculated using a calibration curve created using standard polystyrene. GPC was performed using a column TSKgel Super HM-M manufactured by Tosoh Corporation, at a column temperature of 40 ° C. Tetrahydrofuran was used as the eluent at a flow rate of 0.6 ml / min, and measurements were made with a refractive index detector.

[0129] [Production of Curable Resin] [Example 1] 175 g of D-NDM (a mixture of approximately 1:1 of decahydro-1,4:5,8-dimethanonaphthalene-2,6(7)-dimethanol represented by the following formulas (8) and (9)), 7.7 g of maleic anhydride, and 0.015 g of tetra-n-butyl titanate were placed in a 500 ml separable flask and gradually heated to 200°C while stirring under a nitrogen flow, and maintained until no more distilled water was produced. Thereafter, the pressure was gradually reduced to 13 kPa, and the mixture was maintained for 30 minutes and allowed to cool to room temperature. Thereafter, 163 g of diphenyl carbonate was added, and the temperature and pressure were gradually increased, and polymerization was finally carried out at 230°C and 0.1 kPa or less. As a result, curable resin A was obtained. The number average molecular weight of curable resin A was 5,000.

[0130]

[0131] Example 2 A curable resin B was obtained in the same manner as in Example 1, except that the amount of diphenyl carbonate used was 160 g. The number average molecular weight of the curable resin B was 5,000.

[0132] [Example 3] Curable resin C was obtained in the same manner as in Example 1, except that 219 g of D-NDM, 19 g of maleic anhydride, 0.018 g of tetra-n-butyl titanate, and 181 g of diphenyl carbonate were used. The number average molecular weight of curable resin C was 5,000.

[0133] Example 4 216 g of TCDDM (tricyclodecane dimethanol represented by the following formula (10)), 9.8 g of maleic anhydride, and 0.020 g of tetra-n-butyl titanate were placed in a 500 ml separable flask and gradually heated to 165°C while stirring under a nitrogen flow, and maintained until no more distilled water was produced. The pressure was then gradually reduced to 13 kPa, maintained for 30 minutes, and allowed to cool to room temperature. 226 g of diphenyl carbonate was then added, and the temperature and pressure were gradually increased, and polymerization was finally carried out at 230°C and 0.1 kPa or less. Curable resin D was thus obtained. The number average molecular weight of curable resin D was 4,800.

[0134]

[0135] [Example 5] 175 g of D-NDM, 152 g of diphenyl carbonate, and 0.015 g of tetra-n-butyl titanate were placed in a 500 ml separable flask, and the temperature and pressure were gradually increased while stirring under a nitrogen flow, and polymerization was finally carried out at 230 ° C and 0.1 kPa or less. After cooling to room temperature, 7.7 g of maleic anhydride was added, and the temperature was increased to 200 ° C and maintained until no more water was distilled out. Thereafter, the pressure was gradually reduced to 13 kPa, and the mixture was maintained for 30 minutes to carry out polymerization, thereby obtaining a curable resin E. The number average molecular weight of the curable resin E was 5,000.

[0136] [Example 6] 137 g of 1,4-cyclohexanedimethanol, 183 g of diphenyl carbonate, and 0.0097 g of tetra-n-butyl titanate were placed in a 500 ml separable flask, and the temperature and pressure were gradually increased and reduced while stirring under a nitrogen flow, and polymerization was finally carried out at 230 ° C and 0.1 kPa or less. After cooling to room temperature, 9.3 g of maleic anhydride was added, and the temperature was increased to 200 ° C and maintained until no more water was distilled out. Thereafter, the pressure was gradually reduced to 13 kPa, and the temperature was maintained for 30 minutes to carry out polymerization, thereby obtaining curable resin H. The number average molecular weight of curable resin H was 5,000.

[0137] [Comparative Example 1] 151 g of propylene glycol, 93 g of maleic anhydride, and 140 g of phthalic anhydride were placed in a 500 ml separable flask, and the temperature was raised to 200°C while stirring under a nitrogen flow and maintained until no more water was distilled. Thereafter, the pressure was gradually reduced to 13 kPa, and the temperature was maintained for 30 minutes to obtain curable resin F, which is an unsaturated polyester resin.

[0138] Comparative Example 2 222 g of D-NHEs (decahydro-1,4:5,8-dimethanonaphthalene-2-methoxycarbonyl-6(7)-methanol), 9.0 g of maleic anhydride, and 0.020 g of tetra-n-butyl titanate were placed in a 500 ml separable flask. While stirring under a nitrogen flow, the temperature was gradually increased and the pressure was gradually reduced, and polymerization was finally carried out at 280°C and 0.1 kPa or less to obtain a curable resin G.

[0139] [Evaluation of Curable Resins] (Method for Measuring Dielectric Constant and Dielectric Loss Tangent) Rod-shaped samples of cured resin compositions were prepared in the following Examples 7 to 17 and Comparative Examples 3 to 5. The dielectric constant and dielectric loss tangent of the samples at 10 GHz were measured using a cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies).

[0140] [Example 7] 5.6 g of the curable resin A produced above, 1.9 g of tricyclodecanol acrylate, and 0.075 g of Perbutyl P (manufactured by NOF Corporation) were dissolved in toluene to obtain a 20 wt% solution. The solution was then placed in a vacuum dryer and dried at room temperature for 48 hours and at 60°C for 3 hours to remove the toluene. After the toluene was removed, the resin composition was placed in a 1 mm thick mold, sandwiched between an Aflex film (manufactured by AGC Corporation) and a SUS plate, and placed in a vacuum press heated to 200°C. －２ After reducing the pressure to 100 kPa, the mold was gradually pressurized to 0.6 MPa and heated for 90 minutes, after which the mold was removed and slowly cooled. After slowly cooling, the cured resin composition was removed from the mold. The removed cured material was cut into 0.8 mm wide rod-shaped samples. The cut samples were dried in a vacuum dryer at 70°C for one day, after which the dielectric constant and dielectric loss tangent were measured. The results are shown in Table 1.

[0141] [Examples 8 to 17: Comparative Examples 3 to 5] Rod-shaped samples were prepared in the same manner as in Example 7, except that the resin compositions were blended in the amounts of components shown in Table 1 or Table 2. The measurement results of the dielectric constant and dielectric loss tangent are shown in Tables 1 and 2.

[0142]

[0143]

[0144] [Example 18] The dielectric constant and dielectric loss tangent of curable resin A alone were calculated from the results of Examples 7 and 10 to 13. Specifically, the proportional equation between the content of each component and the dielectric constant and dielectric loss tangent was calculated, and the dielectric constant and dielectric loss tangent of curable resin A alone were found. The dielectric constant and dielectric loss tangent of curable resin A alone were calculated to be 2.4 and 0.003, respectively.

[0145] [Production and Evaluation of Further Curable Resins] Furthermore, curable resins I, J, and K were produced in the following Examples 19, 20, and 21, respectively. In Examples 22, 23, and 24, rod-shaped samples were prepared as cured products of resin compositions containing curable resins I, J, and K, respectively. The dielectric constant and dielectric loss tangent of the samples at 10 GHz were measured using a cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies).

[0146] [Example 19] PCDDM (pentacyclo[6.5.1.1] represented by the following formula (12) ３，６ .0 ２，７ .0 ９，１３ 44.7 g of pentadecanedimethanol, 1.7 g of maleic anhydride, and 0.0030 g of tetra-n-butyl titanate were placed in a 500 ml separable flask and gradually heated to 200°C while stirring under a nitrogen flow. The mixture was maintained until no more water was distilled. The pressure was then gradually reduced to 13 kPa, maintained for 30 minutes, and allowed to cool to room temperature. 35.1 g of diphenyl carbonate was then added, and the temperature and pressure were gradually increased, and polymerization was finally carried out at 230°C and 0.1 kPa or less. Thus, curable resin I was obtained. The number average molecular weight of curable resin I was 4,300.

[0147]

[0148] Example 20 44.2 g of hydrogenated BisA (hydrogenated bisphenol A represented by the following formula (13)), 1.8 g of maleic anhydride, and 0.0030 g of tetra-n-butyl titanate were placed in a 500 ml separable flask and gradually heated to 200°C while stirring under a nitrogen flow, and maintained until no more water was distilled. The pressure was then gradually reduced to 13 kPa, maintained for 30 minutes, and allowed to cool to room temperature. 38 g of diphenyl carbonate was then added, and the temperature and pressure were gradually increased, and polymerization was finally carried out at 230°C and 0.1 kPa or less. Curable resin J was thus obtained. The number average molecular weight of curable resin J was 2,000.

[0149]

[0150] Example 21 44.2 g of TMC (4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol represented by the following formula (14)), 1.8 g of maleic anhydride, and 0.0030 g of tetra-n-butyl titanate were placed in a 500 ml separable flask and gradually heated to 200°C while stirring under a nitrogen flow, and maintained until no more water was distilled. The pressure was then gradually reduced to 13 kPa, maintained for 30 minutes, and allowed to cool to room temperature. 38 g of diphenyl carbonate was then added, and the temperature and pressure were gradually increased, and polymerization was finally carried out at 230°C and 0.1 kPa or less. Curable resin K was thus obtained. The number average molecular weight of curable resin K was 2,000.

[0151]

[0152] Examples 22 to 24 Rod-shaped samples were prepared in the same manner as in Example 7, except that the resin compositions were blended in the amounts of components shown in Table 3. The measurement results of the dielectric constant and dielectric loss tangent are shown in Table 3.

[0153]

Claims

1. It includes a structural unit represented by the following formula (1), a structural unit represented by the following formula (2), and a structural unit represented by the following formula (3), The molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) is 0.010 or more and 0.50 or less. A curable resin in which the molar ratio of structural units represented by formula (3) to structural units represented by formula (2) is 0.50 or more and 1.5 or less. 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 (In the above formula (1), R 1 R is a divalent group having at least one of an ethylenic double bond and an acetylene triple bond, and in formula (2) above, 2 (It is a divalent group with an alicyclic structure.)

2. The curable resin according to claim 1, wherein the molar ratio of the sum of the content of structural units represented by formula (1), structural units represented by formula (2), and structural units represented by formula (3) to all structural units constituting the curable resin is 0.60 or more and 1.0 or less.

3. The curable resin according to claim 1, wherein the structural unit represented by formula (3) is derived from at least one selected from the group consisting of dialkyl carbonate, diaryl carbonate, and alkylaryl carbonate.

4. The curable resin according to claim 1, wherein the structural unit represented by formula (1) is derived from at least one selected from the group consisting of fumaric acid, maleic acid, and maleic anhydride.

5. The curable resin according to claim 1, wherein the structural unit represented by formula (2) is derived from a dihydroxy compound comprising at least one selected from the group consisting of norbornane skeletons and cyclohexane skeletons.

6. The curable resin according to claim 1, wherein the molar ratio of structural units represented by formula (1) to structural units represented by formula (2) is 0.010 or more and less than 0.

30.

7. The curable resin according to claim 1, wherein the molar ratio of structural units represented by formula (3) to structural units represented by formula (2) is 0.80 or more and 1.5 or less.

8. The number-average molecular weight is 5.00 × 10⁻⁶. 2 The above 3.00 x 10 4 The curable resin according to claim 1, which is as follows:

9. The curable resin according to claim 1, comprising a polyester portion that includes a structural unit represented by formula (1) and a structural unit represented by formula (2), but does not include a structural unit represented by formula (3).

10. The curable resin according to claim 1, wherein the dielectric loss tangent calculated according to the measurement method including (i) to (iii) below is 0.010 or less. (i) Prepare a cured product of the resin composition containing the curable resin, and measure the dielectric loss tangent of the cured product at 10 GHz. (ii) The same measurements as in (i) are performed on multiple cured products in which the content of each component of the resin composition is changed. (iii) The dielectric loss tangent of the curable resin alone is calculated by extrapolating the measurement results of (i) and (ii) above.

11. A cured product of the curable resin according to claim 1.

12. A resin composition comprising the curable resin described in claim 1.

13. The resin composition according to claim 12, wherein the content of the curable resin is 1.0 part by mass or more per 100 parts by mass of the resin component.

14. A method for producing the curable resin described in Claim 1, A method for producing a compound, comprising reacting at least one of the compound represented by the following formula (4) and the compound represented by the following formula (4') with the compound represented by the following formula (5) and the compound represented by the following formula (6). 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 (In the above formula (4), R 1 is a divalent group having at least one ethylene double bond and one acetylene triple bond, R 3 and R 4 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms. In the above formula (4'), R 1 has the same meaning as R 1 in the above formula (4). In the above formula (5), R 2 is a divalent group having an alicyclic structure, R 5 and R 6 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 7 carbon atoms. In the above formula (6), R 7 and R 8 are each independently an arbitrary substituent.)

15. Reacting a compound represented by formula (5) with at least one of the compound represented by formula (4) and the compound represented by formula (4') in a molar equivalent amount less than that of the compound represented by formula (5), A step of reacting the obtained product with the compound represented by formula (6), The manufacturing method according to claim 14, including

16. The resin composition according to claim 12, for use as an electronic material.

17. An electronic component comprising a cured product of the resin composition described in claim 12.

18. A fiber-reinforced composite material comprising the resin composition according to claim 12 and reinforcing fibers.

19. A fiber-reinforced molded article which is a cured product of the fiber-reinforced composite material according to claim 18.

20. A semiconductor encapsulating material comprising the resin composition described in claim 12 and an inorganic filler.

21. A semiconductor device comprising a cured product of the semiconductor encapsulation material described in claim 20.

22. A prepreg comprising a base material and a resin composition according to claim 12 impregnated or coated onto the base material.

23. A laminate comprising the prepreg described in claim 22.

24. A circuit board comprising a laminate according to claim 23 and metal foil disposed on one or both sides of the laminate.

25. A build-up film comprising a cured product of the resin composition according to claim 12 and a base film.

26. The curable resin according to claim 1, wherein the structural unit represented by formula (2) is derived from a dihydroxy compound containing a norbornane skeleton.

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