JP2024012085A - Polymer compounds, resin compositions, resin films, prepregs, laminates, printed wiring boards, and semiconductor packages - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: polymer compounds excellent in solvent solubility, heat resistance, and a low dielectric constant; and resin compositions, resin films, prepregs, laminates, printed wiring boards, and semiconductor packages.

SOLUTION: The polymer compounds comprise a repeating unit represented by the general formula (1) in the figure. In the general formula (1), X is a divalent organic group, and the broken lines are bonds.)

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present disclosure relates to a polymer compound, a resin composition, a resin film, a prepreg, a laminate, a printed wiring board, and a semiconductor package.

The amount of data communication from communication terminals such as smartphones continues to increase. Communication frequencies are becoming increasingly high in order to transmit large amounts of data in a short time. In order to raise the communication frequency, it is necessary to suppress transmission loss. Materials with low dielectric constants are needed to suppress transmission losses. Porous polyimide films, resins having cyanato groups, resins having maleimide groups, and the like have been proposed as materials with low dielectric constants. A porous polyimide membrane is disclosed in Patent Document 1. A resin having a cyanato group is disclosed in Patent Document 2. A resin having a maleimide group is disclosed in Patent Document 3.

Japanese Patent Application Publication No. 2015-042718 JP2015-106628A Patent No. 5030297

Depending on the use of the material, in addition to a low dielectric constant, solvent solubility and heat resistance may be required. With the materials disclosed in Patent Documents 1 to 3, it is difficult to simultaneously satisfy low dielectric constant, solvent solubility, and heat resistance. Low dielectric constant property is a property of low dielectric constant.

In one aspect of the present disclosure, it is possible to provide a polymer compound, a resin composition, a resin film, a prepreg, a laminate, a printed wiring board, and a semiconductor package that are excellent in low dielectric constant, solvent solubility, and heat resistance. preferable.

One aspect of the present disclosure is a polymer compound containing a repeating unit represented by the following general formula (1). (In general formula (1), X is a divalent organic group. The broken line is a bond.)

The polymer compound of the present disclosure has excellent low dielectric constant properties, solvent solubility, and heat resistance.
Another aspect of the present disclosure is a polymer compound containing a repeating unit represented by the following general formula (2). (In general formula (2), X is a divalent organic group. The broken line is a bond.)

The polymer compound of the present disclosure has excellent low dielectric constant properties, solvent solubility, and heat resistance.
Another aspect of the present disclosure is a polymer compound containing a repeating unit represented by the following general formula (3). (In general formula (3), X is a divalent organic group. The broken line is a bond.)
The polymer compound of the present disclosure has excellent low dielectric constant properties, solvent solubility, and heat resistance.

Another aspect of the present disclosure is a polymer compound containing a repeating unit represented by the following general formula (4). (In general formula (4), X is a divalent organic group. The broken line is a bond.)

The polymer compound of the present disclosure has excellent low dielectric constant properties, solvent solubility, and heat resistance.
Another aspect of the present disclosure is a repeating unit represented by the following general formula (1), a repeating unit represented by the following general formula (2), a repeating unit represented by the following general formula (3), and the following general formula It is a polymer compound containing one or more types of repeating units selected from the group consisting of repeating units represented by formula (4). (In general formulas (1) to (4), X is a divalent organic group. The broken line is a bond.)

The polymer compound of the present disclosure has excellent low dielectric constant properties, solvent solubility, and heat resistance.

FIG. 2 is an explanatory diagram showing a method for producing a polymer compound. FIG. 2 is an explanatory diagram showing a method for producing a polymer compound. FIG. 2 is an explanatory diagram showing the chemical reactions that occur during the synthesis of maleamic acid 1. FIG. 2 is an explanatory diagram showing a process of synthesizing maleimide resin 1.

Exemplary embodiments of the present disclosure will be described with reference to the drawings.
1. Structure of Polymer Compound The polymer compounds of the present disclosure include polymer compounds P1 to P5. The polymer compound P1 includes a repeating unit represented by the following general formula (1). In general formula (1), X is a divalent organic group. The dashed lines are bonds.

The polymer compound P2 includes a repeating unit represented by the following general formula (2). In general formula (2), X is a divalent organic group. The dashed lines are bonds.

The polymer compound P3 includes a repeating unit represented by the following general formula (3). In general formula (3), X is a divalent organic group. The dashed lines are bonds.

The polymer compound P4 includes a repeating unit represented by the following general formula (4). In general formula (4), X is a divalent organic group. The dashed lines are bonds.

The polymer compound P5 includes a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (2), a repeating unit represented by the general formula (3), and the general formula ( Contains one or more repeating units selected from the group consisting of repeating units represented by 4).

X in general formulas (1) to (4) and general formulas (13) to (14) described below is represented by any of the following structural formulas (8-1) to (8-21). It is preferable that there be.

In structural formulas (8-1) to (8-21), the bond to which no substituent is bonded is the nitrogen atom in general formulas (1) to (4) or general formulas (13) to (14). It is combined with
X can be selected from among the substituents represented by structural formulas (8-1) to (8-21) as appropriate depending on the physical properties required for the polymer compounds P1 to P5.

When X is a substituent represented by Structural Formula (8-8) or Structural Formula (8-9), the cured film prepared using any of the polymer compounds P1 to P5 is flexible, Because it is highly flexible and has excellent low dielectric constant properties, it is particularly useful as a material for insulating films and adhesive sheets.

X in general formulas (1) to (4) and general formulas (13) to (14) described below may be represented by the following general formula (19).

In general formula (19), the bond to which no substituent is bonded is a nitrogen atom in a repeating unit represented by any of general formulas (1) to (4), or general formulas (13) to It bonds with the nitrogen atom in the compound represented by any one of (14). n is any natural number from 1 to 100. A is independently a tetravalent organic group containing a cyclic structure. B and Q are each independently a divalent organic group. B and Q may be the same or different.

A is preferably represented by any of the following structural formulas (20-1) to (20-18) and structural formulas (21-1) to (21-8).

In Structural Formulas (20-1) to (20-18) and Structural Formulas (21-1) to (21-8), the bond to which no substituent is bonded has a cyclic imide structure in General Formula (19). It bonds with the carbonyl carbon formed. X1 in structural formula (21-2) is an oxygen atom, a sulfur atom, a sulfonyl group, or a divalent organic group having 1 to 3 carbon atoms. X2 in structural formula (21-3) is an oxygen atom, a sulfur atom, a sulfonyl group, a divalent organic group having 1 to 3 carbon atoms, or an arylene group. A is basically the same as that represented by Structural Formula (21-2), but does not have X1, and the two carbon atoms to which X1 is bonded in Structural Formula (21-2) are They may be directly bonded. A is basically the same as that represented by Structural Formula (21-3), but it does not have X2, and the two carbon atoms to which X2 is bonded in Structural Formula (21-3) are They may be directly bonded.

B and Q in general formula (19) are each preferably represented by one of the above structural formulas (8-1) to (8-21).
In structural formulas (8-1) to (8-21), the bond to which no substituent is bonded is a nitrogen atom in a repeating unit represented by any of general formulas (1) to (4), Alternatively, it is a compound that bonds with a nitrogen atom in a compound represented by any of the general formulas (13) to (14).

Examples of B and Q in general formula (19) include those represented by any of the following structural formulas (22-1) to (22-6).

The polyimide structure of the compound represented by general formula (19) is highly flexible and flexible. Therefore, when X is represented by the general formula (19), the cured film produced using any of the polymer compounds P1 to P5 will also be highly flexible and pliable. When X is represented by the general formula (19), a cured film prepared using any of the polymer compounds P1 to P5 is preferable as a material for use in an insulating film or an adhesive sheet.

When B and Q in general formula (19) are substituents represented by structural formula (8-8) or structural formula (8-9), the The cured film is not only highly flexible and pliable, but also has excellent low dielectric constant properties, and is therefore particularly preferred as a material for use in insulating films and adhesive sheets.

The polymer compounds P1 to P5 further include, for example, a repeating unit represented by the following general formula (5).

In the general formula (5), R ¹ is a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms which may be substituted with halogen, or a straight chain which may be substituted with halogen. A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be substituted with halogen.

Examples of the repeating unit represented by general formula (5) include, but are not limited to, those represented by any of the following structural formulas (9-1) to (9-43).

The polymer compounds P1 to P5 further include, for example, a repeating unit represented by the following general formula (6) or the following general formula (7).

In the general formula (6), R ² is a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms which may be substituted with halogen, or a straight chain which may be substituted with halogen. A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be substituted with halogen. a is an integer from 0 to 6.

In the general formula (7), R ³ is a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms which may be substituted with halogen, or a straight chain which may be substituted with halogen. A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be substituted with halogen. b is an integer from 0 to 4.

Examples of the repeating unit represented by general formula (6) include, but are not limited to, those represented by any of the following structural formulas (10-1) to (10-5).

Examples of the repeating unit represented by general formula (7) include, but are not limited to, those represented by any of the following structural formulas (11-1) to (11-13).

When the polymer compounds P1 to P5 further contain a repeating unit represented by any of the general formulas (5) to (7) as a copolymer unit, the polymer compounds P1 to P5 have low dielectric constant properties and solvent dissolution. The properties and heat resistance are further improved.

The polymer compounds P1 to P5 contain one of the repeating units represented by general formula (5), the repeating units represented by general formula (6), and the repeating units represented by general formula (7). It may be included or two or more types may be included.

In the polymer compounds P1 to P5, the mol% ratio of repeating units represented by any of the general formulas (1) to (4) is defined as ma. In the polymer compounds P1 to P5, the mol% ratio of repeating units represented by any of the general formulas (5) to (7) is defined as mb.

Preferably, 1<ma<99 and 1<mb<99. More preferably, 5<ma<95 and 5<mb<95. More preferably, 10<ma<90 and 10<mb<90. When ma and mb have such a ratio, the low dielectric constant properties and heat resistance of the polymer compounds P1 to P5 are further improved.

The mass average molecular weights of the polymer compounds P1 to P5 are not particularly limited. The mass average molecular weight of the polymer compounds P1 to P5 is preferably 500 to 50,000, more preferably 700 to 30,000, and still more preferably 1,000 to 20,000. When the mass average molecular weight of the polymer compounds P1 to P5 is within this range, it is possible to suppress the viscosity of the resin composition containing the polymer compounds P1 to P5 from becoming excessively high, and the cured product of the resin composition has high strength. It also has excellent heat resistance.

The polymer compounds P1 to P5 further include one or more repeating units selected from the group consisting of, for example, α-olefin units, cycloolefin units, and vinyl ether units.

An α-olefin unit is an alkene terminated by a carbon-carbon double bond. The α-olefin unit is preferably one or more selected from the group consisting of a linear α-olefin, a branched α-olefin, and a cyclic α-olefin, and more preferably a linear α-olefin.

The number of carbon atoms in the α-olefin unit is preferably 2 or more, more preferably 6 or more and 50 or less, particularly preferably 10 or more and 30 or less. Specifically, α-olefin units include ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene. , 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and the like.

Examples of the cycloolefin unit include norbornene compounds such as norbornene, methylnorbornene, dimethylnorbornene, ethylnorbornene, ethylidenenorbornene, and butylnorbornene.

Examples of the cycloolefin unit include dicyclopentadiene compounds such as dicyclopentadiene, dihydrodicyclopentadiene, methyldicyclopentadiene, and dimethyldicyclopentadiene.

Furthermore, examples of the cycloolefin unit include tetracyclododecene, methyltetracyclododecene, dimethylcyclotetradodecene, tricyclopentadiene, and tetracyclopentadiene.

The monocyclic olefin is not particularly limited. Examples of the monocyclic olefin include cyclobutene, cyclopentene, cyclooctene, cyclooctadiene, cyclooctatriene, and cyclododecatriene.

Among these, norbornene is preferred from the viewpoint of easy availability of raw material monomers and easy improvement of heat resistance.

Examples of vinyl ether units include alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, and 2-ethylhexyl vinyl ether.

When the polymer compounds P1 to P5 further include one or more repeating units selected from the group consisting of α-olefin units, cycloolefin units, and vinyl ether units as copolymerized units, the polymer compounds P1 to P5 The flexibility and fluidity of the resin composition are further improved, and the resin composition has a low viscosity, which is advantageous in producing a low-viscosity resin composition. Moreover, the flexibility and toughness of the resin film created using the resin composition are further improved.

The polymer compounds P1 to P5 may contain one type of repeating unit selected from the group consisting of an α-olefin unit, a cycloolefin unit, and a vinyl ether unit, or may contain two or more types of repeating units. You can stay there.

In the polymer compounds P1 to P5, the mol% ratio of repeating units represented by any of the general formulas (1) to (4) is defined as ma. In the polymer compounds P1 to P5, mb is the mol% ratio of one or more repeating units selected from the group consisting of α-olefin units, cycloolefin units, and vinyl ether units.

Preferably, 1<ma<99 and 1<mb<99. More preferably, 5<ma<95 and 5<mb<95. Particularly preferably, 10<ma<90 and 10<mb<90. When ma and mb have such a ratio, the low dielectric constant properties and heat resistance of the polymer compounds P1 to P5 are further improved, and the flexibility and toughness of the resin film using them are also further improved.

The mass average molecular weights of the polymer compounds P1 to P5 are not particularly limited. The mass average molecular weight of the polymer compounds P1 to P5 is preferably 500 to 50,000, more preferably 700 to 30,000, particularly preferably 1,000 to 20,000. When the mass average molecular weight of the polymer compounds P1 to P5 is within this range, it is possible to suppress the viscosity of the resin composition containing the polymer compounds P1 to P5 from becoming excessively high, and the cured product of the resin composition has high strength. It also has excellent heat resistance.

2. Method for Producing Polymer Compounds Polymer compounds P1 to P5 can be produced, for example, by the method shown in FIG. Step (1) in FIG. 1 involves reacting a resin containing maleic anhydride units represented by general formula (0) (hereinafter referred to as precursor resin) with a compound represented by general formula (13). , is a step of obtaining a polymer compound P2. In general formula (13), X is a divalent organic group. The dashed lines are bonds.

The polymer compound P2 includes a repeating unit represented by general formula (2).
The reaction in step (1) can be carried out in a solvent. In the reaction of step (1), heating and cooling may be performed as necessary. Solvents that can be used in the reaction in step (1) include ethers such as tetrahydrofuran (THF), diethyl ether, diisopropyl ether, di-n-butyl ether, and 1,4-dioxane, n-hexane, n-heptane, and benzene. , hydrocarbons such as toluene and xylene, aprotic polar solvents such as acetonitrile, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMAC), methylene chloride, and chloroform. , chlorine-based organic solvents such as carbon tetrachloride, and the like.

These solvents may be appropriately selected and used depending on the reaction conditions, and may be used alone or in a mixture of two or more.
The reaction temperature in step (1) is preferably -20 to 150°C, more preferably 0 to 120°C. The reaction time in step (1) is preferably 5 minutes to 24 hours, more preferably 1 to 20 hours.

The amount of the compound represented by general formula (13) is preferably 0.1 to 5 equivalents, more preferably 0.2 to 3 equivalents, and 0.1 to 5 equivalents, more preferably 0.2 to 3 equivalents, relative to the amount of maleic anhydride units in the precursor resin. More preferably 5 to 2.5 equivalents.

After the reaction in step (1), the reaction may proceed to step (2) without any particular purification step, but it is desirable to go through a purification step in order to avoid unwanted side reactions in the next step.
The polymer compound P2 is obtained by separating the reaction mixture of step (1) using a known separation means for organic compounds. For example, the polymer compound P2 can be obtained by pouring the reaction mixture in which the polymer compound P2 is formed into water to precipitate a solid, filtering the solid, and drying it as appropriate.

The purity of the polymer compound P2 can be increased by further purifying the polymer compound P2 obtained in this manner by a known purification means for organic compounds, if necessary.

Step (2) is a step of dehydrating and ring-closing the polymer compound P2 obtained in step (1). The reaction in step (2) can be carried out in a solvent. In step (2), heating and cooling may be performed as necessary. Furthermore, in step (2), water produced as a by-product during the reaction may be discharged out of the system by azeotropy with the solvent.

Solvents that can be used in the reaction in step (2) include ethers such as tetrahydrofuran (THF), diethyl ether, diisopropyl ether, di-n-butyl ether, and 1,4-dioxane, n-hexane, n-heptane, and benzene. , hydrocarbons such as toluene and xylene, aprotic polar solvents such as acetonitrile, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMAC), methylene chloride, and chloroform. , chlorine-based organic solvents such as carbon tetrachloride, and the like.

Further, in step (2), an acid or a base may be used as a catalyst to promote the dehydration reaction. Moreover, the acidic catalyst used in the reaction of step (2) is not particularly limited. Examples of the acidic catalyst used in the reaction in step (2) include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and phosphoric acid. The amount of the acid catalyst used is usually 0.1 to 50% by weight, preferably 1 to 25% by weight, based on the weight of the polymer compound P2.

The polymer compound P1 is obtained by separating the reaction mixture in step (2) using a known separation means for organic compounds. For example, the polymer compound P1 can be obtained by pouring the reaction mixture in which the polymer compound P1 is formed into water to precipitate a solid, filtering the solid, and drying it as appropriate. The purity of the polymer compound P1 can be increased by further purifying the polymer compound P1 obtained in this way, if necessary, by a known purification means for organic compounds.

In step (2), by adjusting any one of the reaction temperature, reaction time, and catalyst amount as necessary, the ring closure of the amic acid possessed by the polymer compound P2 does not proceed completely, and only one % may be left as an amic acid. By doing so, any one of the polymer compounds P3 to P5 can be obtained in step (2). By selecting the reactive organism in step (2) from among the polymer compounds P1, P3 to P5, the physical properties of the reactive organism in step (2) can be adjusted. Examples of the physical properties to be adjusted include dielectric properties and heat resistance.

The polymer compounds P1 to P5 can be produced, for example, by the method shown in FIG. Step (3) shown in FIG. 2 can be performed under the same conditions as step (1). However, in step (3), the precursor resin and the compound represented by general formula (14) are reacted. In general formula (14), X is a divalent organic group. The dashed lines are bonds.

The reaction product of step (3) is a polymer compound P3. Step (4) can be performed under the same conditions as step (2).
In step (4), by adjusting any one of the reaction temperature, reaction time, and catalyst amount as necessary, the ring closure of the amic acid possessed by the polymer compound P3 does not proceed completely, but only once. % may be left as an amic acid. By doing so, in step (4), one of the polymer compounds P1, P3, and P5 is obtained. By selecting the reactive organism in step (4) from among the polymer compounds P1, P3, and P5, the physical properties of the reactive organism in step (4) can be adjusted. Examples of the physical properties to be adjusted include dielectric properties and heat resistance.

As a method for synthesizing the precursor resin, there is a method of dissolving maleic anhydride and a monomer to be copolymerized in an organic solvent, adding a radical polymerization initiator, and performing heating polymerization to obtain the precursor resin.

Examples of the organic solvent used in the above synthesis method include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, methyl ethyl ketone, methyl isobutyl ketone, Ipsol 100 (manufactured by Idemitsu Kosan Co., Ltd.), and the like.

As the radical polymerization initiator used in the above synthesis method, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2- methyl propionate), benzoyl peroxide, lauroyl peroxide, and the like.

The polymerization temperature in the above synthesis method is preferably 50 to 250°C. The reaction time in the above synthesis method is preferably 2 to 100 hours, more preferably 3 to 20 hours.

After the polymerization reaction is completed, the thermally melted precursor resin can be taken out as a solid while distilling off the organic solvent. Alternatively, the precursor resin may be taken out by adding the polymerization solution to a poor solvent such as hexane, and filtering and drying the precipitated precursor resin.

The precursor resin further includes, for example, a repeating unit represented by any one of general formulas (5) to (7) as a monomer to be copolymerized. In this case, the polymer compounds P1 to P5 produced from the precursor resin also further contain repeating units represented by any of the general formulas (5) to (7).

The precursor resin further includes, for example, one or more repeating units selected from the group consisting of α-olefin units, cycloolefin units, and vinyl ether units as monomers to be copolymerized. In this case, the polymer compounds P1 to P5 produced from the precursor resin further contain repeating units selected from the group consisting of α-olefin units, cycloolefin units, and vinyl ether units.

3. Effects of polymer compounds The polymer compounds P1 to P5 are excellent in low dielectric constant, solvent solubility, and heat resistance. A resin composition containing the polymer compounds P1 to P5 can be produced. A cured product of such a resin composition has a low dielectric constant and a low dielectric loss tangent, and also has excellent heat resistance.

Using the polymer compounds P1 to P5, resin films, prepregs, laminates, printed wiring boards, and semiconductor packages can be manufactured. In that case, the resin film, prepreg, laminate, printed wiring board, and semiconductor package have excellent low dielectric constant properties and heat resistance.

Since polymer compounds P1 to P5 have excellent solvent solubility, when manufacturing resin compositions, resin films, prepregs, laminates, printed wiring boards, and semiconductor packages using polymer compounds P1 to P5, polymer Compounds P1 to P5 are easy to handle.

4. Resin Composition The resin composition of the present disclosure includes any one of polymer compounds P1 to P5. Therefore, the dielectric constant of the cured product of the resin composition of the present disclosure is low. The resin composition of the present disclosure may contain any of the polymer compounds P1 to P5 as is, or may contain a substance modified from the polymer compounds P1 to P5. The substance changed from the polymer compounds P1 to P5 is, for example, a substance produced by a chemical reaction of any of the polymer compounds P1 to P5.

Preferably, the resin composition of the present disclosure further contains an amine compound. As the amine compound, an amine compound having a primary amino group is preferred. The amine compound is preferably at least one selected from the group consisting of monoamine compounds and diamine compounds.

The amine compound may be an aliphatic amine or an aromatic amine. Aliphatic amines include cycloaliphatic amines. There are no particular restrictions on the aliphatic amine as long as it does not have an aromatic ring in its structure. Examples of aliphatic amines include aliphatic monoamines, aliphatic diamines, alicyclic monoamines, and alicyclic diamines.

The aliphatic group in the aliphatic monoamine and aliphatic diamine may be linear or branched. Examples of aliphatic monoamines include diallylamine and the like. Examples of the aliphatic diamine include hexamethylene diamine, 2,5-dimethylhexamethylene diamine, and the like.

The aromatic amine is not particularly limited as long as it has an aromatic ring somewhere in its structure. The aromatic amine may have an aliphatic hydrocarbon group in part. Examples of aromatic amines include aromatic monoamines, aromatic diamines, and the like.

Examples of the aromatic monoamine include aromatic monoamines represented by the following general formula (X1).

In general formula (X1), R ¹¹ is an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group. R ¹² is an alkyl group having 1 to 5 carbon atoms or a halogen atom. t is an integer of 1 or more. u is an integer from 0 to 4. t and u satisfy 1≦t+u≦5. However, when t is an integer of 2 to 5, the plurality of R ¹¹ 's may be the same or different. Further, when u is an integer of 2 to 4, the plurality of R ^12s may be the same or different.

From the viewpoint of solubility and reactivity, R ¹¹ is preferably a hydroxyl group or a carboxy group. Considering heat resistance, R ¹¹ is more preferably a hydroxyl group. Preferably, t is an integer from 1 to 5. From the viewpoint of lowering the dielectric constant, t is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.

Examples of the alkyl represented by R ¹² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-pentyl group, n-pentyl group, and the like. The alkyl represented by R ¹² is preferably an alkyl group having 1 to 3 carbon atoms.

Examples of the halogen atom represented by R ¹² include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. u is preferably 0 or 1, more preferably 0.
Specific examples of aromatic monoamine compounds include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, and o-aminobenzenesulfonic acid. , m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like.

The aromatic diamine may be an aromatic diamine represented by the following general formula (X2).

In the general formula (X2), X is an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a combination thereof, or -O-. R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 5 carbon atoms, a halogen atom, a hydroxyl group, a carboxy group, or a sulfonic acid group. v and w are each independently an integer of 0 to 4. When v is an integer from 2 to 4, multiple R ^13s may be the same or different. Furthermore, when w is an integer of 2 to 4, the plurality of R ^14s may be the same or different.

Examples of the aliphatic hydrocarbon group represented by X include a methylene group, an ethylene group, a propylene group, a propylidene group, and an isopropylidene group. As the aliphatic hydrocarbon group, a methylene group and an isopropylidene group are preferred.

Examples of the aromatic hydrocarbon group represented by X include a phenylene group and a biphenylylene group. Examples of the group represented by X, which is a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group, include groups represented by any of the following structural formulas (12-1) to (12-5). In structural formulas (12-1) to (12-5), * is a binding site.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ¹³ and R ¹⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group. etc. The alkyl group represented by R ¹³ and R ¹⁴ is preferably an alkyl group having 1 to 3 carbon atoms.

v and w are each independently preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
Specific examples of aromatic diamines include 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4, 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1 , 3-bis[2-(4-aminophenyl)-2-propyl]benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4- Bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 1,3-bis[1-(4-(4-aminophenoxy)phenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-(4-aminophenoxy)phenyl)-1-methylethyl]benzene, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, 4, 4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 3,3'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, bis[4-(4-aminophenoxy) phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 9,9-bis(4-aminophenyl)fluorene, and the like.

The resin composition of the present disclosure preferably further contains a curing accelerator from the viewpoints of heat resistance, flame retardance, and the like. The curing accelerator is not particularly limited. Examples of curing accelerators include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, pyridine, and tributylamine; methylimidazole, phenylimidazole, isocyanate mask imidazole (for example, hexamethylene diisocyanate resin and 2-ethyl-4 tertiary amine compounds; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; dicumyl peroxide, 2,5-dimethyl-2,5- Bis(t-butylperoxy)hexane-3,2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, α,α'-bis(t- Examples include organic peroxides such as diisopropylbenzene (butylperoxy); carboxylic acid salts of metals such as manganese, cobalt, and zinc.

Among these, imidazole compounds, organic peroxides, and carboxylic acid salts are preferred, and organic peroxides are more preferred, from the viewpoint of heat resistance, glass transition temperature, and storage stability. Examples of organic peroxides include t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, and dicumyl peroxide. , di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di-t-hexyl peroxide, t-butylcumyl peroxide and the like.

The content of the curing accelerator in the resin composition is not particularly limited. The mass of the curing accelerator contained in the resin composition is preferably 0.01 to 10% by mass, and 0.1 to 5% by mass, based on the mass of all resin components contained in the resin composition. More preferably, the amount is 0.1 to 3% by mass. The total resin components contained in the resin composition are the components excluding the inorganic filler and organic solvent from the resin composition. By controlling the content of the curing accelerator within such a range, the curability and storage stability of the resin composition become even better.

Further, the resin composition of the present disclosure further includes, for example, a component for printed wiring boards. The component for a printed wiring board is a component contained in an insulating resin composition for a printed wiring board of a typical electronic device. Components for printed wiring boards include, for example, thermosetting resins, elastomers, inorganic fillers, organic fillers, flame retardants, functional resins, ultraviolet absorbers, antioxidants, photopolymerization initiators, optical brighteners, Examples include adhesion improvers and organic solvents. The resin composition of the present disclosure may contain one or more of these components for printed wiring boards.

Examples of the thermosetting resin include tetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, silicone resin, and the like. The resin composition of the present disclosure may contain only one kind of these, or may contain two or more kinds.

Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified acrylonitrile.

The inorganic filler is not particularly limited. Examples of inorganic fillers include silica, alumina, barium sulfate, talc, mica, kaolin, boehmite, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide. , aluminum borate, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, zinc borate, zinc stannate, zinc oxide, titanium oxide, silicon carbide, silicon nitride, boron nitride, clay such as fired clay, glass Examples include short fibers, glass powder, and hollow glass beads. The resin composition of the present disclosure may contain only one kind of these, or may contain two or more kinds.

Examples of the organic filler include organic powder. Examples of the organic powder include silicone powder, tetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.

Examples of flame retardants include phosphorus flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric acid ester compounds, phosphazene, and red phosphorus; inorganic flame retardant additives such as antimony trioxide and zinc molybdate. agent; etc.

Can be blended into insulating resin compositions for printed wiring boards of ordinary electronic devices as functional resins, ultraviolet absorbers, antioxidants, photopolymerization initiators, optical brighteners, adhesion improvers, organic solvents, etc. can use things.

5. Resin Film and Prepreg The resin film of the present disclosure is formed using the resin composition of the present disclosure. As a method for producing a resin film, for example, there is a method in which a resin composition is applied to a release film and then semi-cured by heating or the like to form a film. Semi-curing is, for example, B-staging.

The prepreg of the present disclosure includes the resin composition of the present disclosure. The method for manufacturing prepreg is not particularly limited. Prepreg can be manufactured using a known prepreg manufacturing method. For example, a prepreg can be produced by impregnating or coating a fiber base material with the resin composition of the present disclosure and then semi-curing it by heating or the like. Semi-curing is, for example, B-staging. Moreover, a prepreg can be manufactured by laminating the resin film of the present disclosure on a fiber base material.

The heating temperature when semi-curing the resin composition is preferably a temperature equal to or higher than the boiling point of the organic solvent. When the heating temperature is higher than the boiling point of the organic solvent, the resin composition can be semi-cured and the organic solvent can be efficiently removed. The heating temperature during semi-curing is preferably 80 to 200°C, more preferably 140 to 180°C.

The thickness of the entire prepreg can be adjusted as appropriate depending on the thickness of the inner layer circuit, etc. The thickness of the entire prepreg is preferably 10 to 700 μm, more preferably 10 to 500 μm, even more preferably 10 to 250 μm, and even more preferably 10 to 150 μm from the viewpoint of moldability and workability. This is particularly preferred.

6. Laminate The laminate of the present disclosure includes the prepreg of the present disclosure and metal foil. The laminate includes, for example, a prepreg and metal foils for forming a circuit placed on both sides of the prepreg. The laminate of the present disclosure is a metal-clad laminate.

The metal contained in the metal foil may be copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, or an alloy containing at least one of these metal elements. preferable.

As the alloy, copper-based alloys, aluminum-based alloys, and iron-based alloys are preferred. Examples of copper-based alloys include copper-nickel alloys. Examples of iron-based alloys include iron-nickel alloys. An example of the iron-nickel alloy is 42 alloy. Among these, copper, nickel, and 42 alloy are more preferable as metals, and copper is even more preferable from the viewpoint of availability and cost. The thickness of the metal foil is not particularly limited. The thickness of the metal foil is, for example, 3 to 210 μm, preferably 5 to 140 μm.

7. Printed Wiring Board The printed wiring board of the present disclosure includes the prepreg of the present disclosure or the laminate of the present disclosure. The printed wiring board of the present disclosure can be manufactured, for example, by forming a wiring pattern on the metal-clad laminate of the present disclosure. The method of forming the wiring pattern is not particularly limited. Examples of the method for forming the wiring pattern include known methods such as a subtractive method, a fully additive method, a semi-additive process (SAP), and a modified semi-additive process (m-SAP).

8. Semiconductor Package The semiconductor package of the present disclosure includes the printed wiring board of the present disclosure and a semiconductor element mounted on the printed wiring board. The semiconductor package of the present disclosure can be manufactured by mounting semiconductor elements such as semiconductor chips and memories at predetermined positions on a printed wiring board.

9. Example (9-1) Synthesis of maleamic acid
(i) Synthesis of maleamic acid 1 143 g of 1,4-phenylenediamine was dissolved in 2457 g of THF to prepare a first solution. Further, 130 g of maleic anhydride was dissolved in 197 g of THF to prepare a second solution. The second solution was added dropwise to the first solution over 1 hour at room temperature. Next, the mixture was stirred for 1 hour, and the precipitated solid was collected by filtration. Next, the filtered solid was washed with THF and dried at room temperature under reduced pressure to obtain maleamic acid 1. The yield of maleamic acid 1 was 97%. Maleamic acid 1 is a compound represented by general formula (13), in which X is represented by structural formula (8-10). The chemical reaction that occurs in the synthesis of maleamic acid 1 is the reaction shown in FIG.

(ii) Synthesis of maleamic acid 2 Maleamic acid 2 was synthesized basically in the same manner as the synthesis of maleamic acid 1. However, the same amount of 4,4'-oxydianiline was used instead of 1,4-phenylenediamine. Maleamic acid 2 is represented by structural formula (17). Maleamic acid 2 is a compound represented by general formula (13), in which X is represented by structural formula (8-18).

(iii) Synthesis of maleamic acid 3 Maleamic acid 3 was synthesized basically in the same manner as the synthesis of maleamic acid 1. However, the same amount of Priamine 1075 (manufactured by Croda Japan Co., Ltd.) was used instead of 1,4-phenylenediamine. Additionally, an operation was added to add hexane after the reaction was completed to promote crystallization. Maleamic acid 3 is shown in structural formula (18). Maleamic acid 3 is a compound represented by general formula (13), in which X is represented by structural formula (8-9).

（９－２）マレイミド樹脂の合成
(i)マレイミド樹脂１の合成

(9-2) Synthesis of maleimide resin
(i) Synthesis of maleimide resin 1

In a flask equipped with a stirrer, a reflux tube, and a thermometer, 50.2 g of N,N-dimethylacetamide (DMAC) as a reaction solvent, 5.6 g of maleamic acid 1, and a radical polymerization resin containing maleic anhydride units were placed. 28.1g of SM-1 was charged, and the mixture was stirred at 75°C for 6 hours under a nitrogen atmosphere. Radical polymerization resin SM-1 contained 80 parts by mass of styrene and 20 parts by mass of maleic anhydride. The mass average molecular weight of radical polymerization resin SM-1 was 6,000. Radical polymerization resin SM-1 corresponds to the precursor resin. Styrene corresponds to the repeating unit represented by general formula (5).

After cooling, 308.0 g of water and 35.4 g of hydrochloric acid were added to the reaction solution, washed with crystal water, the precipitated solid was filtered out, and vacuum dried at 70°C to obtain 38.9 g of amic acid resin. Obtained. The yield of amic acid resin was 99%. The amic acid resin corresponds to the polymer compound P2. The step of synthesizing the amic acid resin is step (1) in FIG. The amic acid resin contains a repeating unit represented by general formula (2), where X is represented by structural formula (8-10). The amic acid resin further contains styrene, which is a repeating unit represented by general formula (5).

Next, in a flask equipped with a stirrer, a reflux tube, and a thermometer, 76.2 g of N,N-dimethylacetamide (DMAC) as a reaction solvent, 25.4 g of toluene, 34.3 g of an amic acid resin, and an acidic catalyst were added. 4.2 g of certain p-toluenesulfonic acid and 0.02 g of methoquinone as a polymerization inhibitor were charged, and the mixture was stirred at a temperature of 110° C. for 6 hours under a nitrogen atmosphere.

After cooling, the reaction solution was poured into 0.5 L of water, and the precipitated solid was filtered off and vacuum dried at 70° C. to obtain 27.2 g of NAPMI-SMA resin. The yield of NAPMI-SMA resin was 80%. The obtained NAPMI-SMA resin is referred to as maleimide resin 1.

Maleimide resin 1 corresponds to polymer compound P1. The step of synthesizing the maleimide resin 1 is step (2) in FIG. Maleimide resin 1 is represented by general formula (1), and contains a repeating unit in which X is represented by structural formula (8-10). Maleimide resin 1 further contains styrene, which is a repeating unit represented by general formula (5).
(ii) Synthesis of maleimide resins 2 to 4 Maleimide resins 2 to 4 were synthesized basically in the same manner as the synthesis of maleimide resin 1. However, SM-2 to SM-4 shown in Table 1 were used as precursor resins.

The weight average molecular weights Mw of the precursor resins SM-2 to SM-4 are shown in Table 1. Further, the composition ratios of styrene and maleic anhydride constituting the precursor resins SM-2 to SM-4 are as shown in the column of "Precursor resin composition ratio" in Table 1. Composition ratio means mass ratio. Maleimide resins 2 to 4 have different styrene contents compared to maleimide resin 1. The "acid value" in Table 1 is a value measured by a method based on JIS K-0070:1992.
(iii) Synthesis of maleimide resins 5 and 6 Maleimide resins 5 and 6 were synthesized basically in the same manner as the synthesis of maleimide resin 1. However, in the synthesis of maleimide resin 5, maleamic acid 1 was replaced with maleamic acid 2 in the same molar amount. Furthermore, in the synthesis of maleimide resin 6, maleamic acid 1 was replaced with maleamic acid 3 in the same molar amount. Maleimide resins 5 and 6 correspond to the polymer compound P1.

Maleimide resins 5 and 6 differ from maleimide resin 1 in the following points. In maleimide resin 5, X included in general formula (1) is represented by structural formula (8-18). In maleimide resin 6, X included in general formula (1) is represented by structural formula (8-9).
(iv) Synthesis of maleimide resins 7 to 10 Maleimide resins 7 to 10 were synthesized basically in the same manner as the synthesis of maleimide resin 1. However, in the synthesis of maleimide resins 7 to 10, SM-5 to SM-6 shown in Table 1 were used as precursor resins. The weight average molecular weights Mw of the precursor resins SM-5 to SM-6 are as shown in Table 1. Further, the types and composition ratios of the repeating units constituting the precursor resins SM-5 to SM-6 are as shown in the "Precursor resin composition ratio" column of Table 1. Indene corresponds to the repeating unit represented by general formula (7). Acenaphthylene corresponds to the repeating unit represented by general formula (6).

Furthermore, in the synthesis of maleimide resin 9, maleamic acid 1 was replaced with maleamic acid 2 in the same molar amount. Furthermore, in the synthesis of maleimide resin 10, maleamic acid 1 was replaced with maleamic acid 3 in the same molar amount. Maleimide resins 7 to 10 correspond to the polymer compound P1.

Maleimide resins 7 to 10 differ from maleimide resin 1 in the following points. Maleimide resins 7 and 9 further contain styrene and acenaphthylene in addition to the repeating unit represented by general formula (1). Maleimide resins 8 and 10 further contain styrene and indene in addition to the repeating unit represented by general formula (1).

In maleimide resin 9, X included in general formula (1) is represented by structural formula (8-18). In the maleimide resin 10, X included in general formula (1) is represented by structural formula (8-9).

(v) Synthesis of maleimide resins 11, 16, and 21 Maleimide resins 11, 16, and 21 were synthesized basically in the same manner as the synthesis of maleimide resin 1. However, in the synthesis of maleimide resins 11, 16, and 21, SM-7, 12, and 17 shown in Table 1 were used as precursor resins, respectively. The weight average molecular weights Mw of the precursor resins SM-7, 12, and 17 are shown in Table 1. Further, the types and composition ratios of the repeating units constituting the precursor resins SM-7, 12, and 17 are as shown in the column of "Precursor resin composition ratio" in Table 1.

(vi) Synthesis of maleimide resin 12 A flask equipped with a stirrer, a reflux tube, and a thermometer contains 486.4 g of tetrahydrofuran (THF) as a reaction solvent, 57.7 g of maleamic acid 3, and maleic anhydride units. 35.6 g of radical polymerization resin SM-8 was charged and stirred at 40° C. for 4 hours under a nitrogen atmosphere. Thereafter, 62.2 g of propylene glycol monomethyl ether acetate (PGMEA), 23.3 g of acetic anhydride, and 23.3 g of p-toluenesulfonic acid were charged, and the mixture was stirred at 130° C. for 3 hours under a nitrogen atmosphere. After cooling, 746.4 g of methanol was added, and the precipitated solid was filtered and dried under reduced pressure at 40° C. to obtain 52.0 g of maleimide resin 12. The radical polymerization resin SM-8 contained 70 parts by mass of styrene, 20 parts by mass of maleic anhydride, and 10 parts by mass of 1-decene. The mass average molecular weight of the radical polymerization resin SM-8 was 3,000.

(vii) Synthesis of maleimide resins 13-15, 17-20, and 22-27 Maleimide resins 13-15, 17-20, and 22-27 were synthesized basically in the same manner as the synthesis of maleimide resin 12. However, in the synthesis of maleimide resins 13 to 15, 17 to 20, and 22 to 27, SM-9 to 11, 13 to 16, and 18 to 23 shown in Table 1 were used as precursor resins, respectively. The weight average molecular weights Mw of the precursor resins SM-9 to SM-11, 13 to 16, and 18 to 23 are as shown in Table 1. Further, the types and composition ratios of the repeating units constituting the precursor resins SM-9 to SM-11, 13 to 16, and 18 to 23 are as shown in the column of "Precursor resin composition ratio" in Table 1.

(viii) Synthesis of maleimide resin 28 In a flask equipped with a stirrer, a reflux tube, and a thermometer, 68.4 g of toluene as a reaction solvent, 40.0 g of radical polymerization resin SM-8 containing maleic anhydride units, 62.6 g of priamine 1075 and 25.7 g of p-toluenesulfonic acid were charged, and the mixture was stirred at 110° C. for 4 hours under a nitrogen atmosphere. Thereafter, 22.9 g of maleic anhydride, 15.2 g of toluene, and 5.7 g of para-toluenesulfonic acid were charged, and the mixture was stirred at 110° C. for 4 hours under a nitrogen atmosphere. After cooling, 1000 g of methanol was added, and the precipitated solid was filtered and dried under reduced pressure at 40° C. to obtain 56.5 g of maleimide resin 28. Maleimide resin 28 differs from maleimide resin 12 in its manufacturing method.

(ix) Synthesis of maleimide resin 29 Into a flask equipped with a stirrer, a reflux tube, and a thermometer, 50.5 g of mesitylene, 11.4 g of ethanol, and 7.6 g of pyromellitic anhydride as reaction solvents were charged, and nitrogen The temperature was raised to 80° C. in an atmosphere, and 25.2 g of priamine 1075 and 30.0 g of THF were added dropwise at 80° C. over 30 minutes. Thereafter, the mixture was stirred at 80° C. for 30 minutes under a nitrogen atmosphere. Thereafter, pyromellitic anhydride was added at 80°C, the temperature was raised, and the mixture was stirred at 160°C for 1 hour under a nitrogen atmosphere. Thereafter, the mixture was allowed to cool to 80° C., and 2.0 g of maleic anhydride and 25 g of THF were added dropwise at 80° C. over 15 minutes under a nitrogen atmosphere. Thereafter, a mesitylene solution of maleamic acid 4 was obtained by reacting at 80° C. for 1 hour in a nitrogen atmosphere. Maleamic acid 4 is represented by general formula (13), and X is represented by general formula (19). A in general formula (19) is a residue obtained by removing hydrogen atoms from the 1, 2, 4, and 5 positions of benzene. B and Q in general formula (19) are compounds represented by structural formula (8-8).

To the obtained solution of maleamic acid 4, 7.8 g of SM-1 and 15.0 g of THF were charged at 80° C., and the mixture was stirred at 80° C. for 2 hours under a nitrogen atmosphere. Thereafter, 11.0 g of acetic anhydride and 11.0 g of para-toluenesulfonic acid were charged, and the mixture was stirred at 130° C. for 4 hours under a nitrogen atmosphere. After cooling, 360 g of methanol was added, and the precipitated solid was washed with 360 g of methanol, filtered, and dried under reduced pressure at 40° C. to obtain 34.9 g of maleimide resin 29.

(x) Synthesis of maleimide resin 30 Maleimide resin 30 was synthesized basically in the same manner as maleimide resin 29. However, in the synthesis of maleimide resin 30, instead of using priamine 1075 alone, a mixture of priamine 1075 and isophorone diamine was used. The molar ratio of priamine 1075 and isophoronediamine was 1:1. The total molar amount of priamine 1075 and isophorone diamine was the same as the molar amount of priamine 1075 used in the synthesis of maleimide resin 29.

In the synthesis of maleimide resin 30, maleamic acid 5 was used as an intermediate. Maleamic acid 5 is represented by general formula (13), and X is represented by general formula (19). A in general formula (19) is a residue obtained by removing hydrogen atoms from the 1, 2, 4, and 5 positions of benzene. B in general formula (19) is a compound represented by structural formula (22-3). Q in general formula (19) is a compound represented by structural formula (8-8).

(xi) Synthesis of amic acid group-containing resin 1 Amic acid group-containing resin 1 was synthesized basically in the same manner as the synthesis of maleimide resin 1. However, in the synthesis of maleimide resin 1, stirring was performed at a temperature of 110°C for 6 hours in step (2), but in the synthesis of amic acid group-containing resin 1, stirring was performed at a temperature of 90°C for 1 hour in step (2). did. Amic acid group-containing resin 1 corresponds to polymer compound P5.

Amic acid group-containing resin 1 contains, in addition to the repeating unit represented by general formula (1), the repeating unit represented by general formula (2), the repeating unit represented by general formula (3), and the general formula It differs from maleimide resin 1 in that it contains the repeating unit represented by (4), and X in general formulas (1) to (4) is represented by structural formula (8-10).

(xii) Synthesis of amic acid group-containing resin 2 In a flask equipped with a stirrer, a reflux tube, and a thermometer, 50.2 g of N,N-dimethylacetamide (DMAC) as a reaction solvent and 5.0 g of maleamic acid 1 were added. Then, 28.1 g of radical polymer resin SM-1 containing 6 g of maleic anhydride units was charged, and the mixture was stirred at 75° C. for 6 hours under a nitrogen atmosphere.

After cooling, 308.0 g of water and 35.4 g of hydrochloric acid were added to the reaction solution, washed with crystal water, the precipitated solid was filtered out, and the amic acid group-containing resin 2 was vacuum-dried at 70°C. 38.9g was obtained. The yield of the amic acid group-containing resin 2 was 99%. Amic acid group-containing resin 1 corresponds to polymer compound P2.

Amic acid group-containing resin 2 is represented by general formula (2) instead of the repeating unit represented by general formula (1), and X contains a repeating unit represented by structural formula (8-10). This is different from maleimide resin 1. Amic acid group-containing resin 2, like maleimide resin 1, further contains styrene, which is a repeating unit represented by general formula (5).
(9-3) Production of resin compositions Examples 1 to 37 and Comparative Examples 1 to A resin composition of No. 4 was obtained. The units of amounts of components in Tables 2, 3, and 4 are parts by mass.

The resin compositions of Examples 1 to 12 and Comparative Examples 1 to 2 were cast using a silicone mold and cured at 200° C. for 3 hours to obtain cured products. A test piece with a length of 50 mm, a width of 10 mm, and a thickness of 3 mm was cut out from the obtained cured product and used as a sample for dynamic viscoelasticity measurement. In addition, a prismatic test piece with a length of 80 mm and 1.5 mm square was cut out to serve as a sample for dielectric constant measurement.

In addition, the abbreviations of the compounds in Tables 2, 3, and 4 used in the production of the resin compositions have the following meanings, respectively.
DGEBA...Bisphenol A diglycidyl ether MCHAah...4-methylcyclohexane-1,2-dicarboxylic anhydride MIR-3000...Nippon Kayaku Co., Ltd., biphenylaralkyl maleimide resin BMI-1000... - Evaluation of dielectric properties and heat resistance of 4,4'-diphenylmethane bismaleimide (9-4) The test pieces of Examples 1 to 12 and Comparative Examples 1 to 2 were evaluated as follows.
(i) Relative permittivity and dielectric loss tangent Tests were conducted using a cavity resonator perturbation method using a 10 GHz cavity resonator manufactured by Kanto Denshi Application Development Co., Ltd. The measurement results are shown in Table 2.
(ii) Glass transition temperature Measured using a dynamic viscoelasticity tester. The temperature at which tan δ reached its maximum value was defined as the glass transition temperature. The measurement conditions were as follows. The measurement results are shown in Table 2. The unit of glass transition temperature in Table 2 is °C.

Dynamic viscoelasticity measuring instrument: DMA-800 manufactured by TA-instruments
Temperature rising rate: 4°C/min As shown in Table 2, the dielectric constant and dielectric loss tangent of the resin compositions of Examples 1 to 12 were higher than the dielectric constant and dielectric loss tangent of the resin compositions of Comparative Examples 1 to 2. It was small.
(9-5) Evaluation of solvent solubility Maleimide resins 1 to 4, 11, 15, 17, 20, 23, and 26 and BMI-1000 were used as samples. The sample and methyl ethyl ketone were mixed at a mass ratio of 3:2, and then stirred for 1 hour. Methyl ethyl ketone corresponds to the solvent.

If a transparent solution was created after stirring, the sample was evaluated to have good solvent solubility. Further, if there was any undissolved sample after stirring, the solvent solubility of the sample was judged to be poor. The evaluation results are shown in Table 5. In Table 5, "○" means that the solvent solubility is good, and "x" means that the solvent solubility is poor.

（９－６）フィルム状硬化物の誘電特性評価

(9-6) Evaluation of dielectric properties of film-shaped cured product

The resin compositions of Examples 11 to 37 and Comparative Examples 3 to 4 were used as samples. 1 part by mass of DCPO was added to 100 parts by mass of the sample, and methyl ethyl ketone was used as a solvent to prepare a solution with a solid content concentration of 50%. The solution prepared above was applied to the release-treated PET film using a bar coater. Thereafter, the solvent in the solution was dried at 80°C, and heated at 200°C for 2 hours. After cooling to room temperature, the PET film was peeled off to prepare a sample for dielectric property measurement. The sample for measuring dielectric properties was in the form of a film.

Film forming ability was evaluated according to the following criteria. Note that 〇 means an evaluation result that is better than ×. The evaluation results are shown in Tables 3 and 4. The resin compositions of Examples 11 to 37 were excellent in film forming ability.

○: A film-like sample for dielectric property measurement was able to be created by the above operation.
×: A film-like sample for dielectric property measurement could not be created by the above operation.
The values of the relative dielectric constant and the dielectric loss tangent were measured by the cavity resonator perturbation method using a 10 GHz cavity resonator manufactured by Kanto Denshi Application Development Co., Ltd. The measurement results are shown in Tables 4 and 5.
As shown in Tables 3 and 4, the cured films made from maleimide resins 2 to 7 and 11 to 30 had higher dielectric constants and dielectric loss tangents than the cured films made from the resin compositions of Comparative Examples 3 and 4. It was confirmed that the value of In addition, with the resin compositions of Comparative Examples 3 and 4, it was not possible to create a film using the same method as with the resin compositions of Examples 11 to 37. A prismatic test piece with a length of 80 mm and 1.5 mm square was cut out from the molded cured product and used as a sample for dielectric constant measurement.

10. Other Embodiments Although the embodiments of the present disclosure have been described above, the present disclosure is not limited to the above-described embodiments and can be implemented with various modifications.

(1) The function of one component in each of the above embodiments may be shared among multiple components, or the function of multiple components may be performed by one component. Further, a part of the configuration of each of the above embodiments may be omitted. Further, at least a part of the configuration of each of the above embodiments may be added to, replaced with, etc. in the configuration of other embodiments.

(2) In addition to the above-mentioned polymer compounds, the present disclosure can also be realized in various forms, such as products containing the polymer compounds as constituent elements, and methods for producing polymer compounds.
[Technical idea disclosed in this specification]
[Item 1]
A polymer compound containing a repeating unit represented by the following general formula (1).
(In general formula (1), X is a divalent organic group. The broken line is a bond.)

［項目２］

[Item 2]

A polymer compound containing a repeating unit represented by the following general formula (2).
(In general formula (2), X is a divalent organic group. The broken line is a bond.)

［項目３］

[Item 3]

A polymer compound containing a repeating unit represented by the following general formula (3).
(In general formula (3), X is a divalent organic group. The broken line is a bond.)

［項目４］

[Item 4]

A polymer compound containing a repeating unit represented by the following general formula (4).
(In general formula (4), X is a divalent organic group. The broken line is a bond.)

［項目５］

[Item 5]

A repeating unit represented by the following general formula (1), a repeating unit represented by the following general formula (2), a repeating unit represented by the following general formula (3), and a repeating unit represented by the following general formula (4) A polymer compound containing one or more repeating units selected from the group consisting of repeating units.
(In general formulas (1) to (4), X is a divalent organic group. The broken line is a bond.)

［項目６］

[Item 6]

The polymer compound according to any one of items 1 to 5,
A polymer compound further comprising a repeating unit represented by the following general formula (5).
(In the general formula (5), R ¹ is a hydrogen atom, a halogen atom, a linear, branched, or cyclic acyloxy group having 2 to 8 carbon atoms that may be substituted with halogen, or an acyloxy group that may be substituted with halogen) A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be substituted with halogen.)

［項目７］

[Item 7]

The polymer compound according to any one of items 1 to 6,
A polymer compound further comprising a repeating unit represented by the following general formula (6) or the following general formula (7).
(In general formula (6), R ² is a hydrogen atom, a halogen atom, a linear, branched, or cyclic acyloxy group having 2 to 8 carbon atoms that may be substituted with halogen, or an acyloxy group that may be substituted with halogen) A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be substituted with halogen.a is 0 to It is an integer of 6.)
(In general formula (7), R ³ is a hydrogen atom, a halogen atom, a linear, branched, or cyclic acyloxy group having 2 to 8 carbon atoms that may be substituted with halogen, or an optionally halogen-substituted acyloxy group) A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be substituted with halogen. b is 0 to It is an integer of 4.)

［項目８］

[Item 8]

The polymer compound according to any one of items 1 to 5,
A polymer compound further comprising one or more repeating units selected from the group consisting of α-olefin units, cycloolefin units, and vinyl ether units.
[Item 9]
The polymer compound according to any one of items 1 to 8,
A polymer compound in which the X is a divalent organic group represented by any of the following general formulas (8-1) to (8-21).

［項目１０］

[Item 10]

The polymer compound according to any one of items 1 to 8,
A polymer compound in which the X is represented by the following general formula (19).

(In general formula (19), the bond to which no substituent is bonded is a nitrogen atom in a repeating unit represented by any of general formulas (1) to (4), or general formula (13) ~(14). n is a natural number from 1 to 100. A is independently a tetravalent compound containing a cyclic structure. (B and Q are each independently a divalent organic group. B and Q may be the same or different.)

（一般式（１）～（４）、（１３）～（１４）においてＸは２価の有機基である。破線は結合手である。）
［項目１１］

(In the general formulas (1) to (4) and (13) to (14), X is a divalent organic group. The broken line is a bond.)
[Item 11]

A resin composition comprising the polymer compound according to any one of items 1 to 10.
[Item 12]
The resin composition according to item 11,
A resin composition further containing an amine compound or a peroxide.
[Item 13]
A resin film formed using the resin composition according to item 11 or 12.
[Item 14]
A prepreg comprising the resin composition according to item 11 or 12.
[Item 15]
A laminate comprising the prepreg according to item 14 and metal foil.
[Item 16]
A printed wiring board comprising the prepreg according to item 14.
[Item 17]
A printed wiring board comprising the laminate according to item 15.
[Item 18]
The printed wiring board described in item 16,
A semiconductor package comprising: a semiconductor element mounted on the printed wiring board;
[Item 19]
The printed wiring board described in item 17,
A semiconductor package comprising: a semiconductor element mounted on the printed wiring board;

Claims (19)

A polymer compound containing a repeating unit represented by the following general formula (1).
(In general formula (1), X is a divalent organic group. The broken line is a bond.)

A polymer compound containing a repeating unit represented by the following general formula (2).
(In general formula (2), X is a divalent organic group. The broken line is a bond.)

A polymer compound containing a repeating unit represented by the following general formula (3).
(In general formula (3), X is a divalent organic group. The broken line is a bond.)

A polymer compound containing a repeating unit represented by the following general formula (4).
(In general formula (4), X is a divalent organic group. The broken line is a bond.)

A repeating unit represented by the following general formula (1), a repeating unit represented by the following general formula (2), a repeating unit represented by the following general formula (3), and a repeating unit represented by the following general formula (4) A polymer compound containing one or more repeating units selected from the group consisting of repeating units.
(In general formulas (1) to (4), X is a divalent organic group. The broken line is a bond.)

The polymer compound according to any one of claims 1 to 5,
A polymer compound further comprising a repeating unit represented by the following general formula (5).
(In the general formula (5), R ¹ is a hydrogen atom, a halogen atom, a linear, branched, or cyclic acyloxy group having 2 to 8 carbon atoms that may be substituted with halogen, or an acyloxy group that may be substituted with halogen) A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be substituted with halogen.)

The polymer compound according to any one of claims 1 to 5,
A polymer compound further comprising a repeating unit represented by the following general formula (6) or the following general formula (7).
(In general formula (6), R ² is a hydrogen atom, a halogen atom, a linear, branched, or cyclic acyloxy group having 2 to 8 carbon atoms that may be substituted with halogen, or an acyloxy group that may be substituted with halogen) A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be substituted with halogen.a is 0 to It is an integer of 6.
In the general formula (7), R ³ is a hydrogen atom, a halogen atom, a linear, branched or cyclic acyloxy group having 2 to 8 carbon atoms which may be substituted with halogen, or a straight chain which may be substituted with halogen. A linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms which may be substituted with halogen. b is an integer from 0 to 4. )

The polymer compound according to any one of claims 1 to 5,
A polymer compound further comprising one or more repeating units selected from the group consisting of α-olefin units, cycloolefin units, and vinyl ether units. The polymer compound according to any one of claims 1 to 5,
A polymer compound in which the X is a divalent organic group represented by any of the following general formulas (8-1) to (8-21).

The polymer compound according to any one of claims 1 to 5,
A polymer compound in which the X is represented by the following general formula (19).

(In general formula (19), the bond to which no substituent is bonded is a nitrogen atom in a repeating unit represented by any of general formulas (1) to (4), or general formula (13) ~(14). n is a natural number from 1 to 100. A is independently a tetravalent compound containing a cyclic structure. (B and Q are each independently a divalent organic group. B and Q may be the same or different.)

(In the general formulas (1) to (4) and (13) to (14), X is a divalent organic group. The broken line is a bond.) A resin composition comprising the polymer compound according to any one of claims 1 to 5. The resin composition according to claim 11,
A resin composition further containing an amine compound or a peroxide. A resin film formed using the resin composition according to claim 11. A prepreg comprising the resin composition according to claim 11. A laminate comprising the prepreg according to claim 14 and metal foil. A printed wiring board comprising the prepreg according to claim 14. A printed wiring board comprising the laminate according to claim 15. The printed wiring board according to claim 16,
A semiconductor package comprising: a semiconductor element mounted on the printed wiring board; The printed wiring board according to claim 17,
a semiconductor element mounted on the printed wiring board;
A semiconductor package comprising:

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