Polymer-containing resin composition and polymer

Abstract

Provided is a resin composition giving films having excellent dielectric characteristics, the resin composition including a linear polymer which has a repeating unit structure represented by formula (1) and no maleimide group and containing no inorganic particles. In the formula, the X moieties each independently represent an allyl group or a vinyl group and Z represents a divalent group selected from the group consisting of formulae (z1) to (z9) (in the formulae, each black dot "." indicates a bond with the benzene ring).

Description

Resin composition containing polymer and polymer

[0001] The present invention relates to a resin composition containing a polymer and the polymer. The present invention further relates to a resin composition that can be suitably used particularly for underfill applications in semiconductor packages.

[0002] In recent years, with the increase in the amount of information processed and the communication speed of various electronic devices, packaging technologies such as the high integration of the semiconductor devices, the high density of wiring, and the multi-layering of the semiconductor devices have been rapidly advancing. The insulating resin materials used in the semiconductor components (semiconductor packages and semiconductor modules) that make up semiconductor devices are required to have low relative permittivity and low dielectric loss tangent in order to increase the transmission speed of high-frequency signals and reduce loss during signal transmission. For example, the underfill and molding resins used in semiconductor packages are required to have excellent low dielectric properties (in this invention, a low dielectric loss tangent is referred to as "excellent dielectric properties").

[0003] Methods for filling underfill material include a pre-supply method in which the underfill material is first applied or formed by film bonding onto the metal bumps of a semiconductor device and then bonded to another substrate or semiconductor device, and a post-supply method (capillary underfill method) in which the underfill material is filled into the gap after bonding the substrates or semiconductor devices. Generally, the insulating layer is formed by curing a resin composition. Examples of such resin compositions include those disclosed in Patent Documents 1 and 2.

[0004] Resin compositions used in known underfill materials include acrylic resins, epoxy resins, and silicone resins, but they have a heat resistance of only about 250°C and cannot be used at temperatures above 250°C. Patent Document 3 and other publications disclose that compounds using aromatic polyether ether ketones are useful as adhesives exhibiting high heat resistance. Patent Document 4 also discloses that a cured product of a resin composition containing a polyether ether ketone compound having a maleimide group and an inorganic filler has a low dielectric constant and dielectric loss tangent and is useful as an insulating layer for printed wiring boards of semiconductor devices.

[0005] Furthermore, from the perspective of improving the connection reliability of devices, underfill is required to function as a stress relief material when stresses such as temperature cycles, impacts, and bending are applied after mounting on the board, and further improvements in its mechanical properties are also required.

[0006] International Publication No. 2022-130575 Patent No. 6800140 Patent No. 5790945 Patent No. 7443975

[0007] The present invention has been made in consideration of the above circumstances, and aims to provide a resin composition and a polymer that give a film having excellent dielectric properties, and also to provide a resin composition and a polymer that give a film having excellent mechanical properties (low coefficient of linear thermal expansion (CTE)), as one of the preferred embodiments of the resin composition.

[0008] As a result of extensive research to achieve the above object, the present inventors have found that a resin composition containing a linear polymer having a specific repeating unit structure and no maleimide groups, optionally containing a crosslinking agent, and containing no inorganic particles, can provide a film with excellent dielectric properties and an appropriate coefficient of linear thermal expansion (CTE), and that a resin composition containing a linear polymer having a specific repeating unit structure and no maleimide groups, and a crosslinking agent, and containing no inorganic particles, can provide a film with a low CTE. They have also found that these films are useful as underfills for semiconductor packages, and have completed the present invention.

[0009] That is, the present invention provides the following resin composition and polymer: 1. A resin composition containing a linear polymer having a repeating unit structure represented by the following formula (1) and having no maleimide group, and containing no inorganic particles. [(In the formula, each X independently represents an allyl group or a vinyl group, and Z represents a divalent group selected from the group consisting of the following formulas (z1) to (z9)] (wherein the black circle "." represents a bond to a benzene ring.) 2. The resin composition of 1 further containing a crosslinking agent. 3. The resin composition of 1 or 2, wherein the polymer further has a repeating unit structure represented by the following formula (2): (wherein Z has the same meaning as above, R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitro group, or a cyano group; a and b each represent the number of substituents and may be 0; when a is 2 or more, a plurality of R 1 may be the same or different and may be bonded in any combination to form a part of a ring structure, and when b is 2 or more, multiple R 2 may be the same or different and may be bonded in any combination to form part of a ring structure, and e and f each independently represent an integer of 0 to 2. 4. The resin composition of any one of 1 to 3, wherein the formula (1) is a repeating unit structure represented by the following formula (1-1): (wherein Z has the same meaning as above) 5. The resin composition of 3 or 4, wherein the formula (2) is a repeating unit structure represented by the following formula (2-1): 6. The resin composition of any one of 2 to 5, wherein the crosslinking agent is a maleimide compound or a polyfunctional (meth)acrylate compound. 7. The resin composition of 1, wherein the polymer is a linear polymer having a repeating unit structure represented by the following formula (P1) and a repeating unit structure represented by the following formula (P2), and does not have a maleimide group, and further contains a crosslinking agent, but does not contain inorganic particles. (In the formula, m is 0.5≦m<1.) [(wherein Z represents a divalent group selected from the group consisting of the following formulae (z1) to (z9), R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitro group, or a cyano group; a and b each represent the number of substituents and may be 0; when a is 2 or more, a plurality of R 1 may be the same or different and may be bonded in any combination to form a part of a ring structure, and when b is 2 or more, multiple R 2may be the same or different and may be bonded in any combination to form a part of a ring structure, e and f each independently represent an integer of 0 to 2, and m has the same meaning as above. (In the formula, the black circle "." represents a bond to the benzene ring.) 8. The resin composition of 7, wherein the formula (P2) is a repeating unit structure represented by the following formula (P2-1): (wherein m has the same meaning as above.) 9. The resin composition of 7 or 8, wherein the crosslinking agent is a maleimide compound or a polyfunctional (meth)acrylate compound. 10. The resin composition of any of 7 to 9, wherein the content of the crosslinking agent is 0.01 to 10 relative to 1 of the polymer, in mass ratio. 11. The resin composition of any of 1 to 10, further comprising a solvent. 12. The resin composition of any of 1 to 11, which is used for underfill. 13. A film obtained from the resin composition of any of 1 to 10. 14. A film obtained from the resin composition of 11. 15. A semiconductor element having a substrate, an IC chip electrically connected via electrodes on the substrate, and an underfill filling the space between the substrate and the IC chip, wherein the underfill is a cured product of the resin composition of 12. 16. An LED display device having a substrate, an LED chip electrically connected via electrodes on the substrate, and an underfill filling the space between the substrate and the LED chip, wherein the underfill is a cured product of the resin composition of 12. 17. A polymer having a repeating unit structure represented by the following formula (A): 18. Film obtained from polymer 17.

[0010] According to the present invention, it is possible to provide a resin composition and a polymer that can provide a film having excellent dielectric properties and an appropriate coefficient of linear thermal expansion (CTE). It is also possible to provide a resin composition and a polymer that can provide a film having excellent mechanical properties (low CTE). These films are useful as underfills for semiconductor packages.

[0011] [1] Resin Composition The resin composition of the present invention contains a predetermined polymer and optionally a crosslinking agent, but does not contain inorganic particles.

[0012] [Polymer] The resin composition of the present invention contains, as the polymer, a linear polymer having a repeating unit structure represented by the following formula (1) and having no maleimide groups in the main chain, side chains or terminals.

[0013]

[0014] In the formula, each X independently represents an allyl group or a vinyl group, with an allyl group being preferred in the present invention.

[0015] In the formula, Z represents a divalent group selected from the group consisting of the following formulae (z1) to (z9):

[0016] (In the formula, the black circle "." represents a bond to the benzene ring.)

[0017] In the present invention, among the above formulas (z1) to (z9), formulas (z1) to (z3) and (z5) to (z9) are preferred, and in consideration of low dielectric properties, formulas (z8) and (z9) are more preferred.

[0018] A preferred embodiment of the repeating unit structure represented by the above formula (1) is a repeating unit structure represented by the following formula (1x), and a repeating unit structure represented by the following formula (1-1) is more preferred.

[0019] (In the formula, X and Z have the same meanings as above.)

[0020] (In the formula, Z has the same meaning as above.)

[0021] Specific examples of the repeating unit structure represented by the above formula (1) include repeating unit structures represented by the following formulas (1-1-1) and (1-1-2), but are not limited thereto.

[0022]

[0023] In the present invention, from the viewpoint of raw material stability, the repeating unit structure represented by formula (1-1-1) is more preferred among these.

[0024] From the viewpoint of improving solubility, the polymer may further have a repeating unit structure represented by the following formula (2).

[0025]

[0026] In the formula, Z has the same meaning as above, and R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitro group, or a cyano group; a and b each represent the number of substituents and may be 0; when a is 2 or more, a plurality of R 1 may be the same or different and may be bonded in any combination to form a part of a ring structure, and when b is 2 or more, multiple R 2 may be the same or different and may be bonded in any combination to form a part of a ring structure; e and f each independently represent an integer of 0 to 2.

[0027] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

[0028] The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n- Examples of such groups include linear or branched alkyl groups having 1 to 20 carbon atoms, such as an octadecyl group, an n-nonadecyl group, or an n-eicosanyl group; and cyclic alkyl groups having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a bicyclobutyl group, a bicyclopentyl group, a bicyclohexyl group, a bicycloheptyl group, a bicyclooctyl group, a bicyclononyl group, or a bicyclodecyl group.

[0029] Examples of the aromatic group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, a 1-biphenyl group, and a 2-biphenyl group.

[0030] Examples of the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, and decyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; bicycloalkyl groups such as bicyclohexyl; alkenyl groups such as vinyl, 1-propenyl, 2-propenyl (allyl), 1-methyl-2-propenyl, 1-, 2-, or 3-butenyl, and hexenyl; aryl groups such as phenyl, xylyl, tolyl, biphenyl, and naphthyl; and aralkyl groups such as benzyl, phenylethyl, and phenylcyclohexyl, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms.

[0031] Specific examples of the halogenated hydrocarbon group include a chloromethyl group, a chloropropyl group, a bromoethyl group, and a trifluoropropyl group.

[0032] Multiple R 1 or R 2 When these bond to form a part of a ring structure, examples of the ring structure include, but are not limited to, ring structures represented by the following formulas (a1) to (a4).

[0033]

[0034] In view of the ease of availability of the raw material compounds, a and b are both preferably 0. In view of the ease of availability of the raw material compounds, e and f are both preferably 0.

[0035] The Z may be a divalent group selected from the group consisting of the formulae (z1) to (z9). The formulae (z1) to (z3) and (z5) to (z9) are preferred, and in consideration of low dielectric properties, the formulae (z8) and (z9) are more preferred.

[0036] A preferred embodiment of the repeating unit structure represented by the above formula (2) is a repeating unit structure represented by the following formula (2x).

[0037] (In the formula, R 11 is a hydrogen atom or R 1 represents R 21 is a hydrogen atom or R 2 Represents Z, R 1 and R 2 has the same meaning as above.)

[0038] Specific examples of the repeating unit structure represented by the above formula (2) include repeating unit structures represented by the following formulas (2-1) and (2-2), but are not limited thereto.

[0039]

[0040] When the polymer contains the repeating unit structure represented by formula (2), the content thereof is preferably 70 mol % or less, more preferably 50 mol % or less, of all repeating units from the viewpoint of film strength. Although there is no particular lower limit, it is preferably 5 mol % or more of all repeating units.

[0041] The weight-average molecular weight of the polymer is preferably about 1,000 to about 1,000,000, more preferably about 3,000 to about 100,000, and even more preferably about 5,000 to about 50,000. The weight-average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0042] The polymer can be synthesized by reacting compounds corresponding to the structure of the target polymer by a known method. When synthesizing a polymer containing a repeating unit structure represented by the above formula (1), for example, a method of appropriately selecting a compound represented by the following formula (3) and a compound represented by the following formula (4) and subjecting them to a nucleophilic substitution reaction can be mentioned.

[0043] (In the formula, Y represents a halogen atom.)

[0044] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

[0045] (In the formula, Z and X are the same as defined in the above formula (1).)

[0046] The compound represented by the formula (3) and the compound represented by the formula (4) may each be used alone or in combination of two or more.

[0047] In the nucleophilic substitution reaction of the two compounds, the compound represented by formula (4) can be used in a ratio of usually 0.1 to 10 moles, preferably 0.1 to 2 moles, per mole of the compound represented by formula (3). The compound represented by formula (4) can be synthesized by the reaction of a bisphenol with an allyl halide, followed by a rearrangement reaction, as described in WO 2013 / 114987.

[0048] Furthermore, when synthesizing a polymer further containing the repeating unit structure represented by the above formula (2), the polymer can be prepared by appropriately selecting a compound represented by the above formula (3), a compound represented by the above formula (4), and a compound represented by the following formula (5) and subjecting them to a nucleophilic substitution reaction.

[0049] (In the formula, Z, R 1 , R 2 , a, b, e, and f are the same as defined in the above formula (2).

[0050] The compound represented by the formula (3), the compound represented by the formula (4), and the compound represented by the formula (5) may each be used alone or in combination of two or more.

[0051] In this nucleophilic substitution reaction, the total amount of the compound represented by the formula (4) and the compound represented by the formula (5) can be set to a ratio of usually 0.1 to 10 moles, preferably 0.1 to 2 moles, relative to 1 mole of the compound represented by the formula (3).

[0052] In the above-mentioned nucleophilic substitution reaction, it is preferable to use a catalyst. In the present invention, a basic or acidic catalyst can be used as the catalyst, but it is preferable to use a basic catalyst. Examples of basic catalysts include solid base catalysts, specific examples of which include calcium hydroxide, strontium hydroxide octahydrate, barium hydroxide octahydrate, magnesium hydroxide, sodium carbonate, and potassium carbonate. Examples of acidic catalysts include mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, and methanesulfonic acid; and carboxylic acids such as formic acid and oxalic acid.

[0053] The amount of the catalyst used varies depending on the type of catalyst used, but is usually 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass, per 100 parts by mass of the compound represented by formula (3).

[0054] The solvent used in polymer synthesis is not particularly limited as long as it can disperse or dissolve the raw materials used. Specific examples of such solvents include ethers such as tetrahydrofuran (THF), diethyl ether, and 1,2-dimethoxyethane (DME); halogenated hydrocarbons such as methylene chloride, chloroform, and 1,2-dichloroethane; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-dimethylpropionamide, N,N-dimethylisobutylamide, and N-methyl-2-pyrrolidone (NMP); ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol. Examples of the solvent include alcohols such as ethanol, aliphatic hydrocarbons such as n-heptane, n-hexane, and cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether, glycols such as ethylene glycol and propylene glycol, carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate, and organic solvents such as γ-butyrolactone, dimethyl sulfoxide (DMSO), dioxolane, and sulfolane. The above solvents may be used alone or in combination of two or more.

[0055] The synthesized polymer may be isolated by dropping the reaction solution into a large amount of poor solvent (for example, water; alcohol such as methanol or isopropanol, or a mixture thereof) to form a precipitate, which is then filtered, washed, and dried. In this case, the reaction solution may be dropped as is, or may be dropped after being appropriately diluted with an appropriate solvent used in the synthesis.

[0056] [Crosslinking Agent] The crosslinking agent is not particularly limited and may be a known one. In the present invention, from the viewpoint of film strength, maleimide compounds and polyfunctional (meth)acrylate compounds are preferred.

[0057] Specific examples of the maleimide compound include N,N'-o-phenylene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, N,N'-(4,4'-diphenylmethane)bismaleimide, 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane, and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane. Among these, 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane is preferred in the present invention. Commercially available products can be used as the maleimide compound.

[0058] Specific examples of the polyfunctional (meth)acrylate compound include 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, neopentyl glycol diacrylate, 2-hydroxy-3-methacrylpropyl acrylate, tricyclodecane dimethanol diacrylate, ethoxylated bisphenol A diacrylate, trimethylolpropane triacrylate, and tris-(2-acryloxyethyl)isocyanurate. Among these, tris-(2-acryloxyethyl)isocyanurate is preferred in the present invention. Commercially available products can be used as the polyfunctional (meth)acrylate compound.

[0059] When the crosslinking agent is contained, the content thereof is, in mass ratio relative to the polymer, preferably 0.01 to 10, more preferably 0.01 to 5, and even more preferably 0.01 to 2.5. The crosslinking agents may be used alone or in combination of two or more.

[0060] When the polymer needs to be dissolved in a crosslinking agent, it is desirable to use a liquid crosslinking agent.

[0061] [Solvent] From the viewpoint of coatability and uniformity of the composition, it is preferable that the resin composition of the present invention further contains a solvent. The solvent is not particularly limited as long as it is one that has conventionally been used in preparing resin compositions for underfilling semiconductor packages. Specific examples thereof include ethers such as tetrahydrofuran (THF), diethyl ether, and 1,2-dimethoxyethane (DME); halogenated hydrocarbons such as methylene chloride, chloroform, and 1,2-dichloroethane; amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N,N-dimethylpropionamide, N,N-dimethylisobutylamide, and N-methyl-2-pyrrolidone (NMP); ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; methanol, ethanol, n-propyl alcohol, and the like. Examples of suitable solvents include alcohols such as propanol, isopropanol, n-butanol, and t-butanol; aliphatic hydrocarbons such as n-heptane, n-hexane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether; glycols such as ethylene glycol and propylene glycol; carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; and organic solvents such as γ-butyrolactone, dimethyl sulfoxide (DMSO), dioxolane, and sulfolane. These solvents may be used alone or in combination of two or more.

[0062] [Thermal Polymerization Initiator] A thermal polymerization initiator can be blended into the resin composition of the present invention in order to promote the thermal polymerization of the polymer and enhance its curability. Examples of the thermal polymerization initiator include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, α,α'-di(tert-butylperoxy)diisopropyl Examples of suitable thermal polymerization initiators include, but are not limited to, α,α'-di(tert-butylperoxybenzene, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl peresters (tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylcyclohexanoate, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), and azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.). Among these, α,α'-di(tert-butylperoxy)diisopropylbenzene is preferred in the present invention. Commercially available products can be used as the thermal polymerization initiator. One of these thermal polymerization initiators can be used alone, or two or more can be used in combination.

[0063] When the thermal polymerization initiator is contained, the content thereof is preferably 0.01 to 0.15, more preferably 0.01 to 0.10, in mass ratio relative to 1 part of the polymer.

[0064] [Other Additives] Furthermore, the resin composition of the present invention may contain, as necessary, other additives such as resin components other than the polymer having the repeating unit structure represented by formula (1) (“other resin components”) and hindered phenol compounds, as long as the effects of the present invention are not impaired.

[0065]

[0013] Furthermore, as one preferred embodiment of the resin composition, the present invention provides a resin composition that contains a linear polymer having a specific repeating unit structure and no maleimide group, and a crosslinking agent, but does not contain inorganic particles. The resin composition will be described in detail below.

[0066] [Polymer] The resin composition contains, as a polymer, a linear polymer having a repeating unit structure represented by the following formula (P1) and a repeating unit structure represented by the following formula (P2), and having no maleimide groups in the main chain, side chain, or terminal.

[0067] (In the formula, m is 0.5≦m<1.)

[0068]

[0069] In the formula, Z represents a divalent group selected from the group consisting of the following formulae (z1) to (z9), and R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitro group, or a cyano group; a and b each represent the number of substituents and may be 0; when a is 2 or more, a plurality of R 1 may be the same or different and may be bonded in any combination to form a part of a ring structure, and when b is 2 or more, multiple R 2 may be the same or different and may be bonded in any combination to form part of a ring structure, and e and f each independently represent an integer of 0 to 2. m has the same meaning as above.

[0070] (In the formula, the black circle "." represents a bond to the benzene ring.)

[0071] From the viewpoint of achieving both dielectric properties and mechanical properties, the above m is preferably 0.5≦m<1.0, and more preferably 0.5≦m≦0.9.

[0072] Of the formulas (z1) to (z9), formulas (z1) to (z3) and (z5) to (z9) are preferred, and in consideration of low dielectric properties, formulas (z8) and (z9) are more preferred.

[0073] Examples of the halogen atom, the alkyl group having 1 to 20 carbon atoms, the aromatic group having 6 to 20 carbon atoms, and the monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms include the same groups as those exemplified in the description of formula (2) above.

[0074] Also, multiple R 1 or R 2 When these bond to form a part of a ring structure, examples of the ring structure include the same ring structures as those exemplified in the explanation of formula (2) above.

[0075] A preferred embodiment of the repeating unit structure represented by the above formula (P2) is a repeating unit structure represented by the following formula (P2x).

[0076] (In the formula, R 11 is a hydrogen atom or R 1 represents R 21 is a hydrogen atom or R 2 Represents Z, R 1 , R 2 and m have the same meaning as above.

[0077] Specific examples of the repeating unit structure represented by the above formula (P2) include repeating unit structures represented by the following formulas (P2-1) and (P2-2), but are not limited thereto.

[0078] (In the formula, m has the same meaning as above.)

[0079] The weight-average molecular weight of the polymer is preferably about 1,000 to about 1,000,000, more preferably about 3,000 to about 100,000, and even more preferably about 5,000 to about 50,000. The weight-average molecular weight is a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0080] The polymer can be synthesized by reacting compounds corresponding to the structure of the target polymer by a known method. When synthesizing a polymer containing the repeating unit structure represented by the formula (P1) and the repeating unit structure represented by the formula (P2), for example, a method of appropriately selecting a compound represented by the formula (3), a compound represented by the formula (4), and a compound represented by the formula (5) and subjecting them to a nucleophilic substitution reaction can be mentioned.

[0081] The compound represented by the formula (3), the compound represented by the formula (4), and the compound represented by the formula (5) may each be used alone or in combination of two or more.

[0082] In this nucleophilic substitution reaction, the total of the compound represented by formula (4) and the compound represented by formula (5) is typically set to a ratio of 0.1 to 10 moles, preferably 0.1 to 2 moles, per mole of the compound represented by formula (3). The ratio of the compound represented by formula (4) and the compound represented by formula (5) may be adjusted to achieve the desired ratio (molar ratio) within the range of m in formula (P1). The compound represented by formula (4) can be synthesized by reacting a bisphenol with an allyl halide, followed by a rearrangement reaction, as described in WO 2013 / 114987.

[0083] In the above-mentioned nucleophilic substitution reaction, it is preferable to use a catalyst. In the present invention, a basic or acidic catalyst can be used as the catalyst, but it is preferable to use a basic catalyst. Examples of the basic catalyst and acidic catalyst include those exemplified above.

[0084] The amount of the catalyst used varies depending on the type of catalyst used, but is usually 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass, per 100 parts by mass of the compound represented by formula (3).

[0085] The solvent used in polymer synthesis is not particularly limited as long as it can disperse or dissolve the raw materials used. Specific examples of such solvents include those exemplified above. The above solvents may be used alone or in combination of two or more.

[0086] The synthesized polymer may be isolated by dropping the reaction solution into a large amount of poor solvent (for example, water; alcohol such as methanol or isopropanol, or a mixture thereof) to form a precipitate, which is then filtered, washed, and dried. In this case, the reaction solution may be dropped as is, or may be dropped after being appropriately diluted with an appropriate solvent used in the synthesis.

[0087] [Crosslinking Agent] The crosslinking agent may be any known agent and is not particularly limited. Specific examples thereof include the same agents as those exemplified above.

[0088] The content of the crosslinking agent is preferably 0.01 to 10, more preferably 0.01 to 5, even more preferably 0.01 to 2.5, and still more preferably 0.1 to 2.5, relative to the polymer 1 in mass ratio. The crosslinking agents may be used alone or in combination of two or more.

[0089] When the polymer needs to be dissolved in a crosslinking agent, it is desirable to use a liquid crosslinking agent.

[0090] [Solvent] The resin composition of the present invention preferably further contains a solvent from the viewpoint of the coatability and uniformity of the composition. Examples of the solvent include the same solvents as those exemplified above. The solvent may be used alone or in combination of two or more.

[0091] [Thermal Polymerization Initiator] A thermal polymerization initiator can be blended into the resin composition to promote the thermal polymerization of the polymer and enhance its curability. Examples of the thermal polymerization initiator include those exemplified above. Commercially available products can be used as the thermal polymerization initiator. Such thermal polymerization initiators can be used alone or in combination of two or more.

[0092] When the thermal polymerization initiator is contained, the content thereof is preferably 0.01 to 0.15, more preferably 0.01 to 0.10, in mass ratio relative to 1 part of the polymer.

[0093] [Other Additives] Furthermore, the resin composition may contain, as necessary, other additives such as resin components other than the polymer having the repeating unit structure represented by formula (P1) and the repeating unit structure represented by formula (P2) (“other resin components”), hindered phenol compounds, etc., as long as the effects of the present invention are not impaired.

[0094] [2] Preparation of Resin Composition The resin composition of the present invention may be prepared by any method, including blending the components in any order. For example, the resin composition may be prepared by dissolving the isolated polymer in a liquid crosslinking agent.

[0095] The composition of the present invention preferably uses a solvent from the viewpoint of improving uniformity and coatability. In this case, the polymer may be used in the form of a polymer solution after the reaction, or may be isolated by removing the solvent. When a solvent different from the solvent used in synthesizing the polymer is used in preparing the resin composition, the solvent may be replaced to obtain the desired solvent system.

[0096] In the present invention, from the viewpoint of reproducibly obtaining a soft-baked film and a fully cured (hardened) film with higher flatness, it is desirable to dissolve each component of the resin composition in a solvent and then filter it using a sub-micron order filter or the like.

[0097] In addition, when the solvent used in the synthesis of the polymer is the same as the solvents exemplified above or a solvent miscible with them, the obtained reaction solution may be used as is. On the other hand, when the solvent used in the synthesis of the polymer is a solvent immiscible with the solvents exemplified above, it is preferable to use the reaction solution obtained by removing the solvent and isolating it, or to use the reaction solution obtained by solvent substitution with an appropriate solvent.

[0098] When the resin composition contains a solvent, the solids concentration of the composition is set appropriately taking into consideration the coatability of the composition, the thickness of the underfill to be formed, etc., but is usually about 1 to 70 mass %, preferably about 5 to 60 mass %, and more preferably about 10 to 50 mass %. The solids content here refers to the components other than the solvent contained in the resin composition of the present invention.

[0099] The viscosity of the resin composition of the present invention is set appropriately taking into consideration the coating method, coatability, thickness of the underfill to be formed, etc., but is usually about 10 to 2,000,000 mPa s, preferably about 30 to 1,000,000 mPa s, and more preferably about 100 to 800,000 mPa s. The above viscosity is a value measured at 25°C using an E-type viscometer.

[0100] The resin composition of the present invention has excellent dielectric properties and is suitable for use as an underfill for semiconductor packages.

[0101] [3] Underfill, Semiconductor Device, and LED Display Device The resin composition of the present invention can be suitably used as an underfill for semiconductor packages, particularly as an underfill used in flip-chip mounting technology in the manufacture of semiconductor devices and LED display devices. Examples of the semiconductor device include a semiconductor device having a substrate, an IC chip (semiconductor chip) electrically connected via electrodes on the substrate, and an underfill filling the gap between the substrate and the IC chip, wherein the underfill is a cured product of the resin composition of the present invention. Examples of the LED display device include an LED display device having a substrate, an LED chip electrically connected via electrodes on the substrate, and an underfill filling the gap between the substrate and the LED chip, wherein the underfill is a cured product of the resin composition of the present invention.

[0102] Such substrates include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0103] The IC chip and LED chip (hereinafter, these may be collectively referred to as "functional chips") may be any known chips, and may be selected appropriately depending on the intended use of the element. Examples of IC chips include ordinary IC chips equipped with processing functions, communication functions, memory functions, etc. Examples of the LED chip include blue LED chips that emit blue light when energized.

[0104] The underfill formed from the cured resin composition of the present invention has excellent dielectric properties and can firmly bond the functional chip to the substrate, preventing the functional chip from falling off the substrate. Furthermore, the underfill has an appropriate coefficient of linear thermal expansion (CTE) and functions as a stress relief material when stresses such as temperature cycles, impacts, and bending are applied after mounting on the substrate. This is expected to improve the durability of the device and the connection reliability between the functional chip and the substrate. While conventional underfills contain inorganic particles to achieve a low CTE, the present invention revises the polymer structure to achieve a practical level of CTE without the inclusion of inorganic particles.

[0105] Furthermore, when a polymer having a repeating unit structure represented by formula (P1) and a repeating unit structure represented by formula (P2) is used, an underfill formed from a cured resin composition containing the polymer can firmly bond the functional chip to the substrate and prevent the functional chip from falling off the substrate. Furthermore, the underfill has a low coefficient of linear thermal expansion (CTE) and functions as a stress relief material when stresses such as temperature cycling, impact, and bending are applied after mounting on the substrate, thereby improving the durability of the device and the connection reliability between the functional chip and the substrate. While conventional compositions contain inorganic particles to achieve a low CTE, the polymer structure of this composition has been redesigned to achieve a CTE lower than the practical level described above without the inclusion of inorganic particles.

[0106] In the above-described element, the method for filling the gap between the functional chip and the substrate with the resin composition of the present invention is not particularly limited, and can be carried out by a known method using, for example, a dispenser. The substrate filled with the resin composition is then heated under predetermined conditions to harden the resin composition filling the gap between the functional chip and the substrate, thereby forming an underfill. The heating conditions in this case may be any conditions that can sufficiently harden the resin composition and do not adversely affect components such as the substrate and functional chip, and are typically about 150 to 300°C for about 1 to 60 minutes.

[0107] Another example of a method is as follows. The resin composition of the present invention is applied to the surface of a solder-bumped substrate on which the solder bumps are formed (a component such as a functional chip is attached to the surface opposite the surface on which the solder bumps are formed), followed by a heat treatment (soft bake) to form a film (soft bake film). The wafer on which the film (soft bake film) is formed is then cut (diced) to the desired size to obtain a chip in which the solder bumps are covered with the film (soft bake film) (hereinafter, also referred to as a "soft bake chip"). The obtained soft bake chip is then placed on another chip on which solder bumps are formed, with the film (soft bake film) side in contact, and the chip is then heated and pressed (fully cured) to harden the film (soft bake film). The film (soft bake film) is completely hardened to form a fully cured film (underfill). At this time, by aligning the solder bumps of the soft bake chip with the solder bumps of another chip, the solder bumps of both chips fuse together and become electrically connected during full curing.

[0108] In this method, the substrate and chips can be the same as those described above, and only the necessary ones can be selected.

[0109] The method for applying the resin composition is not particularly limited, and examples thereof include dipping, spin coating, transfer printing, roll coating, brush coating, inkjet coating, spraying, slit coating, and die coating. It is preferable to adjust the viscosity and surface tension of the composition depending on the application method.

[0110] The thickness of the coating film is not particularly limited as long as it is thick enough to cover the solder bumps, but is usually about 1 to 80 μm.

[0111] The heating conditions for the soft bake may be any conditions that stabilize the shape of the coating film, do not completely cure the film, and do not adversely affect other components such as the substrate and chip, and can usually be about 70 to 150°C for about 0.5 to 10 minutes.

[0112] As the dicing method, known methods such as blade dicing, laser ablation dicing, and stealth dicing can be used, and an appropriate method may be used as needed.

[0113] The heating conditions for full curing may be any conditions that can sufficiently harden the film (soft bake film), push aside the film (soft bake film) covering the surface of the solder bumps, fuse them with the solder bumps of another chip, and do not adversely affect the substrate or other components.

[0114] The resin composition of the present invention can be applied onto a release substrate (e.g., a PET film coated with a silicone release layer) used as a base film by spin coating, bar coating, slit coating, inkjet coating, applicator coating, die coating, gravure coating, knife coating, or the like, and then pre-dried in an oven or the like to form a coating film.

[0115] The conditions for this heat treatment are, for example, a heating temperature and a heating time selected appropriately from the ranges of 70 to 160°C and 0.3 to 60 minutes, respectively. The heating temperature and heating time are preferably 80 to 140°C and 0.5 to 10 minutes.

[0116] Thereafter, a release substrate for a protective film is laminated onto the coating film of the resin composition to obtain an adhesive film. The adhesive film is obtained by pressing the coating film and the protective film together in a certain direction using a manual or automatic laminating roller or vacuum laminating device so as to prevent air bubbles from being trapped between them.

[0117] By processing the adhesive film to a desired size, a film can be formed only in the required locations on a chip or substrate. After processing the adhesive film to a desired size, the protective film is peeled off, the peeled surface is attached to a predetermined location, and the base film is peeled off, thereby transferring the film onto the substrate. To increase the adhesion between the film and the substrate, it is also effective to transfer the film under pressure. To prevent voids between the film and the substrate, it is preferable to laminate under reduced pressure, such as in a vacuum.

[0118] In order to successfully peel the protective film from the coating surface, it is necessary to reduce the peel strength of the protective film and increase the peel strength of the base film. The peel strength of the protective film is preferably 80 mN / 50 mm or less, and the peel strength of the base film is preferably 160 mN / 50 mm or more.

[0119] [4] Polymer The present invention also provides a polymer having a repeating unit structure represented by the following formula (A): Note that with regard to the polymer, the description of the resin composition above can be referred to.

[0120]

[0121] A film having excellent dielectric properties can be obtained from the above polymer.

[0122] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The apparatus and measurement conditions used for the measurements are as follows: Apparatus: GPC system manufactured by JASCO Corporation Column: Shodex (registered trademark) KF-804L and KF-803L Column oven: 40°C Flow rate: 1 mL / min Eluent: tetrahydrofuran Sample concentration: 10 mg / mL Sample injection amount: 20 μL Standard substance: monodisperse polystyrene Detector: differential refractometer

[0123] Synthesis Example 1-1 Synthesis of Polymer (A) A 1,000 mL four-neck flask was charged with 35.0 g (0.16 mol) of 4,4'-difluorobenzophenone, 32.8 g (0.099 mol) of 2,2-bis(3-allyl-4-hydroxyphenyl)propane (Konishi Chemical Industry Co., Ltd., the same applies hereinafter), 35.1 g (0.099 mol) of 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 57.0 g (0.41 mol) of potassium carbonate, and 308.8 g of N-methyl-2-pyrrolidone, and the mixture was heated to 140°C and stirred for 22 hours. After cooling to below 30°C, the mixture was diluted with 102.6 g of tetrahydrofuran, and the precipitate that formed in the reaction solution was removed by filtration to obtain a reaction mixture. The resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid / N-methyl-2-pyrrolidone (1:9) solution, and then added dropwise to a mixed solution of 1,571 g of isopropanol and 392 g of pure water to precipitate a polymer. The resulting precipitate was filtered, and the filter cake was washed twice with 450 g of an isopropanol / water mixed solution in the same ratio as above, and then vacuum dried to obtain a polymer. The molecular weight of this polymer was measured by GPC (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 6,749, and the yield was 100%. This polymer is composed of a repeating unit structure represented by the following formula (A):

[0124]

[0125] Synthesis Example 1-2 (Synthesis of Polymer (B)) A 1,000 mL four-neck flask was charged with 30.0 g (0.14 mol) of 4,4'-difluorobenzophenone, 23.5 g (0.071 mol) of 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 25.1 g (0.071 mol) of 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 48.8 g (0.35 mol) of potassium carbonate, and 235.6 g of N-methyl-2-pyrrolidone, and the mixture was heated to 140°C and stirred for 22 hours. After cooling to below 30°C, the mixture was diluted with 78.2 g of tetrahydrofuran, and the precipitate formed in the reaction solution was removed by filtration to obtain a reaction mixture. The resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid / N-methyl-2-pyrrolidone (1:9) solution, and then added dropwise to a mixed solution of 1,230 g of isopropanol and 307 g of pure water to precipitate a polymer. The resulting precipitate was filtered, and the residue was washed twice with 300 g of an isopropanol / water mixed solution in the same ratio as above, and then vacuum dried to obtain a polymer. The molecular weight of this polymer was measured by GPC (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 26,747, with a yield of 99%. This polymer is composed of a repeating unit structure represented by the above formula (A).

[0126] Synthesis Example 1-3 (Synthesis of Polymer (C)) 20.0 g (0.091 mol) of 4,4'-difluorobenzophenone, 37.5 g (0.11 mol) of 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 32.6 g (0.24 mol) of potassium carbonate, and 172.6 g of N-methyl-2-pyrrolidone were placed in a 1,000 mL four-neck flask, heated to 140°C, and stirred for 22 hours. After cooling to below 30°C, the mixture was diluted with 57.3 g of tetrahydrofuran, and the precipitate formed in the reaction solution was removed by filtration to obtain a reaction mixture. The pH of the resulting reaction mixture was adjusted to 4 with a 6N hydrochloric acid / N-methyl-2-pyrrolidone (1:9) solution, and then added dropwise to a mixture of 882 g of isopropanol and 220 g of pure water to precipitate a polymer. The resulting precipitate was filtered, washed twice with 368 g of an isopropanol / water mixture in the same ratio as above, and then vacuum dried to obtain a polymer. The molecular weight of this polymer was measured by GPC (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 7,668, and the yield was 100%. This polymer is composed of a repeating unit structure represented by the following formula (C):

[0127]

[0128] Comparative Synthesis Example 1-1 (Synthesis of Polymer (X)) A polymer comprising a repeating unit structure represented by the following formula (X) and a terminal structure represented by the following formula (Xa) and a terminal structure represented by the following formula (Xb) was synthesized with reference to the examples in Japanese Patent No. 5790945. The molecular weight of this polymer was measured by GPC (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 8,509.

[0129]

[0130] Example 1-1 3.85 g of the polymer (A) obtained in Synthesis Example 1-1 and 1.65 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K.I. Chemical Co., Ltd.; the same applies hereinafter) were dissolved in 7.58 g of cyclopentanone. The resulting solution was then filtered using a microfilter made of polytetrafluoroethylene (hereinafter abbreviated as PTFE) with a pore size of 5 μm, to obtain a resin composition (solid content concentration 42% by mass).

[0131] Example 1-2 4.40 g of the polymer (A) obtained in Synthesis Example 1-1 and 1.10 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane were dissolved in 5.50 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 50% by mass).

[0132] Example 1-3 4.62 g of the polymer (B) obtained in Synthesis Example 1-2 and 1.98 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane were dissolved in 8.07 g of cyclopentanone, and the solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 45% by mass).

[0133] Example 1-4 4.40 g of the polymer (B) obtained in Synthesis Example 1-2 and 1.10 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane were dissolved in 5.50 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 50% by mass).

[0134] Example 1-5 4.95 g of the polymer (B) obtained in Synthesis Example 2 and 0.55 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane were dissolved in 5.50 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 50% by mass).

[0135] Example 1-6 3.36 g of the polymer (C) obtained in Synthesis Example 1-3 and 1.44 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane were dissolved in 7.20 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 40% by mass).

[0136] Example 1-7 5.50 g of the polymer (B) obtained in Synthesis Example 1-2 was dissolved in 6.73 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 45% by mass). The resin composition of this example does not contain a crosslinking agent.

[0137] Example 1-8 4.29 g of the polymer (B) obtained in Synthesis Example 1-2 and 1.81 g of tris-(2-acryloxyethyl)isocyanurate (A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a crosslinking agent were dissolved in 8.91 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 40% by mass).

[0138] Example 1-9 1.37 g of the polymer (B) obtained in Synthesis Example 1-2, 0.57 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane, and 0.10 g of α,α'-di(tert-butylperoxy)diisopropylbenzene (Perbutyl (registered trademark) P, manufactured by NOF Corporation) as a thermal polymerization initiator were dissolved in 2.99 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 40% by mass).

[0139] Comparative Example 1-1 3.85 g of the polymer (X) obtained in Comparative Synthesis Example 1 and 1.65 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane were dissolved in 5.50 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition.

[0140] [Electrical Property Test] The resin compositions prepared in Examples 1-1 to 1-9 and Comparative Example 1-1 were each applied using a spin coater to aluminum foil laminated on a silicon wafer, soft-baked at 100°C for 5 minutes, and further baked at 250°C under nitrogen for 1 hour to form films (fully cured films) with thicknesses of approximately 10 to 80 μm. The resulting films were then immersed in 6N hydrochloric acid together with the silicon wafer. After immersion in hydrochloric acid, the aluminum foil dissolved, causing the films to peel off from the silicon wafer. The floating portions were collected and cut into 4.6 cm long and 3.5 cm wide pieces to obtain free-standing films. The free-standing films were dried overnight over silica gel, and the relative permittivity and dielectric loss tangent at 60 GHz were calculated immediately after exposure to an atmospheric environment using a split-cylinder cavity resonance method. The measurement results are shown in Table 1 below. Details of the measurement method are as follows. <<Measurement method>> Split cylinder cavity resonance method <<Device configuration>> Vector network analyzer: N5227A PNA network analyzer (manufactured by Keysight Technologies, Inc.) Resonator: CR-710 (manufactured by EM Lab, Inc.) Measurement frequency: Approximately 60 GHz (depending on the resonant frequency of the sample)

[0141]

[0142] [Thermo-mechanical analysis (TMA) measurement] The free-standing film obtained from the resin composition of Example 1-1 above was cut to a width of 5 mm and a length of 20 mm, and the CTE was calculated by TMA measurement. Here, CTE refers to the coefficient of linear thermal expansion, which is the ratio of the deformation amount of the film per 1 K of temperature change to the original length, and the coefficient of linear thermal expansion in the temperature range below the glass transition temperature (Tg) of the free-standing film is designated as CTE1. The measurement results are shown in Table 2 below. The details of the measurement method are as follows. <Apparatus configuration> Thermo-mechanical analyzer: TMA4000SA (manufactured by NETZSCH) Measurement conditions: temperature increase from 30 to 300°C at 5°C / min, tensile mode, nitrogen atmosphere, load -5.0 g

[0143]

[0144] When comparing the free-standing films obtained from the resin compositions of Examples 1-1 to 1-7 with the free-standing film obtained from the resin composition of Comparative Example 1-1, the relative permittivity and dielectric loss tangent of the free-standing films obtained from the resin compositions of Examples 1-1 to 1-7 were clearly lower than those of the free-standing film obtained from the resin composition of Comparative Example 1-1. Furthermore, the free-standing film obtained from the resin composition of Example 1-6, which does not contain the optional repeating unit structure represented by the above formula (2), did not significantly impair the above technical effects and exhibited superior dielectric properties to the free-standing film obtained from the resin composition of Comparative Example 1-1. Furthermore, the free-standing film obtained from the resin composition of Example 1-8, which used a trifunctional acrylate compound instead of a maleimide compound as a crosslinking agent, exhibited a dielectric loss tangent superior to that of Comparative Example 1-1. Furthermore, the free-standing film obtained from the resin composition of Example 1-9, in which a thermal polymerization initiator was added to the resin composition of Example 1-3, exhibited a dielectric loss tangent superior to that of Comparative Example 1-1.

[0145] Synthesis Example 2-1 (Synthesis of Polymer (A1)) A polymer was obtained in the same manner as in Synthesis Example 1-1. The molecular weight of this polymer was measured by GPC (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 6,749, and the yield was 100%. This polymer is composed of a repeating unit structure represented by the following formula (A1). The copolymerization ratio of the polymer is: 1 The values ​​were calculated by measuring using H-NMR (AVANCE III HD (measurement frequency: 500 MHz) manufactured by Bruker).

[0146]

[0147] Synthesis Example 2-2 Synthesis of Polymer (B1) A 500 mL four-neck flask was charged with 10.0 g (0.045 mol) of 4,4'-difluorobenzophenone, 16.89 g (0.051 mol) of 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 2.01 g (0.0057 mol) of 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 16.27 g (0.12 mol) of potassium carbonate, and 86.69 g of N-methyl-2-pyrrolidone, and the mixture was heated to 140°C and stirred for 22 hours. After cooling to below 30°C, the mixture was diluted with 28.79 g of tetrahydrofuran, and the precipitate formed in the reaction mixture was removed by filtration to obtain a reaction mixture. The resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid / N-methyl-2-pyrrolidone (1:9) solution, and then added dropwise to a mixed solution of 443 g of isopropanol and 111 g of pure water to precipitate a polymer. The resulting precipitate was filtered, and the residue was washed twice with 184 g of an isopropanol / water mixed solution in the same ratio as above, and then vacuum dried to obtain a polymer. The molecular weight of this polymer was measured by GPC (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 7,273, and the yield was 99%. This polymer is composed of a repeating unit structure represented by the following formula (B1). The copolymerization ratio of the polymer is: 1 The values ​​were calculated by measuring using H-NMR (AVANCE III HD (measurement frequency: 500 MHz) manufactured by Bruker).

[0148]

[0149] Comparative Synthesis Example 2-1 Synthesis of Polymer (X1) A 500 mL four-neck flask was charged with 20.0 g (0.091 mol) of 4,4'-difluorobenzophenone, 3.53 g (0.011 mol) of 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 33.97 g (0.096 mol) of 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 32.55 g (0.24 mol) of potassium carbonate, and 172.50 g of N-methyl-2-pyrrolidone, and the mixture was heated to 140°C and stirred for 22 hours. After cooling to below 30°C, the mixture was diluted with 57.30 g of tetrahydrofuran, and the precipitate that formed in the reaction solution was removed by filtration to obtain a reaction mixture. The resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid / N-methyl-2-pyrrolidone (1:9) solution, and then added dropwise to a mixed solution of 882 g of isopropanol and 220 g of pure water to precipitate a polymer. The resulting precipitate was filtered, and the residue was washed twice with 368 g of an isopropanol / water mixed solution in the same ratio as above, and then vacuum dried to obtain a polymer. The molecular weight of this polymer was measured by GPC (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 8,782, and the yield was 99%. This polymer is composed of a repeating unit structure represented by the following formula (X1). The copolymerization ratio of the polymer is: 1 The values ​​were calculated by measuring using H-NMR (AVANCE III HD (measurement frequency: 500 MHz) manufactured by Bruker).

[0150]

[0151] Comparative Synthesis Example 2-2 (Synthesis of Polymer (Y1)) A 500 mL four-neck flask was charged with 20.0 g (0.091 mol) of 4,4'-difluorobenzophenone, 10.60 g (0.032 mol) of 2,2-bis(3-allyl-4-hydroxyphenyl)propane, 26.42 g (0.075 mol) of 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, 32.55 g (0.24 mol) of potassium carbonate, and 171.05 g of N-methyl-2-pyrrolidone, and the mixture was heated to 140°C and stirred for 22 hours. After cooling to below 30°C, the mixture was diluted with 56.82 g of tetrahydrofuran, and the precipitate that formed in the reaction mixture was removed by filtration to obtain a reaction mixture. The resulting reaction mixture was adjusted to pH 4 with a 6N hydrochloric acid / N-methyl-2-pyrrolidone (1:9) solution, and then added dropwise to a mixed solution of 876 g of isopropanol and 220 g of pure water to precipitate a polymer. The resulting precipitate was filtered, and the residue was washed twice with 365 g of an isopropanol / water mixed solution in the same ratio as above, and then vacuum dried to obtain a polymer. The molecular weight of this polymer was measured by GPC (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 8,574, and the yield was 99%. This polymer is composed of a repeating unit structure represented by the following formula (Y1). The copolymerization ratio of the polymer is: 1 The values ​​were calculated by measuring using H-NMR (AVANCE III HD (measurement frequency: 500 MHz) manufactured by Bruker).

[0152]

[0153] Preparation Example 1 112.6 g of MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd., a 2-butanone solution of a maleimide compound represented by the following formula (M), solid content 70% by mass) was dissolved in 79.2 g of cyclopentanone. Thereafter, the solvent was replaced at 50 hPa and 40° C., to obtain 148.0 g of a cyclopentanone solution (solid content 52.4% by mass) of a maleimide compound represented by the following formula (M) (hereinafter referred to as maleimide compound (M)).

[0154] (In the formula, n represents the number of repeating units.)

[0155] Example 2-1 3.25 g of the polymer (A1) obtained in Synthesis Example 2-1 and 1.35 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane (manufactured by K.I. Chemical Co., Ltd.; the same applies hereinafter) were dissolved in 5.40 g of cyclopentanone. The resulting solution was then filtered using a polytetrafluoroethylene (hereinafter abbreviated as PTFE) microfilter having a pore size of 5 μm to obtain a resin composition (solid content concentration: 45% by mass).

[0156] Example 2-2 2.97 g of the polymer (A1) obtained in Synthesis Example 2-1 and 1.62 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane were dissolved in 5.41 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 45% by mass).

[0157] Example 2-3 2.78 g of the polymer (A1) obtained in Synthesis Example 2-1 and 1.80 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane were dissolved in 5.42 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 45% by mass).

[0158] Example 2-4 3.25 g of the polymer (B1) obtained in Synthesis Example 2-2 and 1.35 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane were dissolved in 5.40 g of cyclopentanone, and the solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 45% by mass).

[0159] Example 2-5 2.78 g of the polymer (B1) obtained in Synthesis Example 2-2 and 2.27 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane were dissolved in 5.43 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 45% by mass).

[0160] Example 2-6 2.30 g of the polymer (B1) obtained in Synthesis Example 2-2 and 1.80 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane were dissolved in 5.42 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 45% by mass).

[0161] Example 2-7 2.23 g of the polymer (B1) obtained in Synthesis Example 2-2, 2.10 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane, and 0.21 g of α,α'-di(tert-butylperoxy)diisopropylbenzene (Perbutyl (registered trademark) P, manufactured by NOF Corporation; the same applies hereinafter) were dissolved in 5.46 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 45% by mass).

[0162] Example 2-8 1.65 g of the polymer (B1) obtained in Synthesis Example 2-2, 4.74 g of a cyclopentanone solution (solid content 52.4% by mass) of the maleimide compound (M) obtained in Preparation Example 1, and 0.20 g of α,α'-di(tert-butylperoxy)diisopropylbenzene were dissolved in 3.41 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter having a pore size of 5 μm to obtain a resin composition (solid content concentration 45% by mass).

[0163] Example 2-9 1.91 g of the polymer (B1) obtained in Synthesis Example 2-2, 0.98 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane, 2.74 g of a cyclopentanone solution (solids content 52.4% by mass) of the maleimide compound (M) obtained in Preparation Example 1, and 0.21 g of α,α'-di(tert-butylperoxy)diisopropylbenzene were dissolved in 4.16 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter having a pore size of 5 μm to obtain a resin composition (solids content concentration 45% by mass).

[0164] Comparative Example 2-1 4.22 g of the polymer (X1) obtained in Comparative Synthesis Example 2-1 and 0.44 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane were added to 5.35 g of cyclopentanone, but the mixture gelled and did not dissolve.

[0165] Comparative Example 2-2 3.45 g of the polymer (Y1) obtained in Comparative Synthesis Example 2-2 and 1.12 g of 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane were dissolved in 5.43 g of cyclopentanone. The resulting solution was then filtered using a PTFE microfilter with a pore size of 5 μm to obtain a resin composition (solid content concentration: 45% by mass).

[0166] [Thermomechanical analysis (TMA) measurement] The resin compositions prepared in Examples 2-1 to 2-9 and Comparative Examples 2-1 to 2-2 were each applied using a spin coater onto aluminum foil laminated on a silicon wafer, soft-baked at 100°C for 5 minutes, and further baked under nitrogen at 200 to 250°C for 1 to 2 hours to form a film (fully cured film) with a thickness of approximately 10 to 80 μm. The resulting film was then immersed in 6N hydrochloric acid together with the silicon wafer. For each film, after immersion in hydrochloric acid, the aluminum foil dissolved, the film peeled off from the silicon wafer, and the floating part was collected to obtain a free-standing film. The obtained free-standing film was cut to a width of 4 to 5 mm and a length of 20 mm, and the CTE was calculated by TMA measurement. Note that, here, CTE refers to the linear thermal expansion coefficient, which is the ratio of the deformation amount of the film per 1 K temperature change to its original length, and the linear thermal expansion coefficient in the temperature range above the glass transition temperature (Tg) of the free-standing film is designated as CTE2. The measurement results are shown in Table 3 below. Details of the measurement method are as follows: <Device configuration> Thermomechanical analyzer: TMA4000SA (manufactured by NETZSCH) Measurement conditions: temperature increase from 30 to 300°C at 5°C / min, tension mode, nitrogen atmosphere, load -5.0 g

[0167]

[0168] [Electrical Property Test] The resin composition prepared in Examples 2-4 was applied using a spin coater to aluminum foil laminated on a silicon wafer, soft-baked at 100°C for 5 minutes, and further baked at 250°C for 1 hour under nitrogen to form a film (fully cured film) with a thickness of approximately 10 to 80 μm. The resulting film was then immersed in 6N hydrochloric acid together with the silicon wafer. For each film, after immersion in hydrochloric acid, the aluminum foil dissolved, causing the film to peel off from the silicon wafer. The floating portion was collected and cut into a length of 4.6 cm and a width of 3.5 cm to obtain a free-standing film. This free-standing film was dried overnight over silica gel, and the relative permittivity and dielectric loss tangent at 60 GHz immediately after exposure to an atmospheric environment were calculated using a split cylinder cavity resonance method. The measurement results are shown in Table 4 below. The details of the measurement method are as follows. <<Measurement method>> Split cylinder cavity resonance method <<Device configuration>> Vector network analyzer: N5227A PNA network analyzer (manufactured by Keysight Technologies, Inc.) Resonator: CR-710 (manufactured by EM Lab, Inc.) Measurement frequency: Approximately 60 GHz (depending on the resonant frequency of the sample)

[0169]

[0170] In Comparative Example 2-1, gelation occurred during the preparation of the resin composition due to the improved hydrophobicity of the polymer, and a free-standing film could not be prepared. The CTE2 of the free-standing films obtained from the resin compositions of Examples 2-1 to 2-9 was clearly lower than the CTE2 of the free-standing film obtained in Comparative Example 2-2. Furthermore, the CTE2 of the free-standing film obtained from the resin composition of Example 2-7, which used α,α'-di(tert-butylperoxy)diisopropylbenzene as a thermal polymerization initiator, was lower than the CTE2 of the free-standing films obtained in Examples 2-1 to 2-6. Furthermore, the CTE2 of the free-standing film obtained from the resin composition of Example 2-8, which used the maleimide compound (M) obtained in Preparation Example 1 as a crosslinker, was lower than the CTE2 of the free-standing films obtained in Examples 2-1 to 2-7. Furthermore, the CTE2 of the free-standing film obtained from the resin composition of Example 2-9, which used 2,2-bis-[4-(4-maleimidophenoxy)phenyl]propane and the maleimide compound (M) obtained in Preparation Example 1 in combination as a crosslinking agent, also showed a lower value than the CTE2 of the free-standing films obtained in Examples 2-1 to 2-7.

[0171] The resin composition containing the polymer according to the present invention provides an insulating film that exhibits a lower dielectric loss tangent than the free-standing film obtained from the resin composition of Comparative Example 1-1.

Claims

1. A resin composition containing a linear polymer having a repeating unit structure represented by the following formula (1), which does not contain maleimide groups, and which does not contain inorganic particles. [(In the formula, each X independently represents an allyl group or a vinyl group, and Z represents a divalent group selected from the group consisting of the following formulas (z1) to (z9)] (In the formula, the black circle "." represents a bond to the benzene ring.) 2. The resin composition according to claim 1, further comprising a crosslinking agent.

3. The resin composition according to claim 1 or 2, wherein the polymer further has a repeating unit structure represented by the following formula (2): (wherein Z has the same meaning as above, R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitro group, or a cyano group; a and b each represent the number of substituents and may be 0; when a is 2 or more, a plurality of R 1 may be the same or different and may be bonded in any combination to form a part of a ring structure, and when b is 2 or more, multiple R 2 may be the same or different and may be bonded in any combination to form a part of a ring structure, and e and f each independently represent an integer of 0 to 2.

4. The resin composition according to claim 1 or 2, wherein the formula (1) is a repeating unit structure represented by the following formula (1-1): (In the formula, Z has the same meaning as above.) 5. The resin composition according to claim 3, wherein the repeating unit structure of the formula (2) is represented by the following formula (2-1):

6. The resin composition according to claim 2, wherein the crosslinking agent is a maleimide compound or a polyfunctional (meth)acrylate compound.

7. The resin composition according to claim 1, wherein the polymer is a linear polymer having a repeating unit structure represented by the following formula (P1) and a repeating unit structure represented by the following formula (P2), having no maleimide group, further containing a crosslinking agent, and not containing inorganic particles. (In the formula, m is 0.5≦m<1.) [(wherein Z represents a divalent group selected from the group consisting of the following formulae (z1) to (z9), R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a monovalent halogenated hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitro group, or a cyano group; a and b each represent the number of substituents and may be 0; when a is 2 or more, a plurality of R 1 may be the same or different and may be bonded in any combination to form a part of a ring structure, and when b is 2 or more, multiple R 2 may be the same or different and may be bonded in any combination to form a part of a ring structure, e and f each independently represent an integer of 0 to 2, and m has the same meaning as above. (In the formula, the black circle "." represents a bond to the benzene ring.) 8. The resin composition according to claim 7, wherein the formula (P2) is a repeating unit structure represented by the following formula (P2-1): (In the formula, m has the same meaning as above.) 9. The resin composition according to claim 7, wherein the crosslinking agent is a maleimide compound or a polyfunctional (meth)acrylate compound.

10. The resin composition according to claim 7, wherein the content of said crosslinking agent is 0.01 to 10 parts by mass per 1 part of said polymer.

11. The resin composition according to claim 1, 2 or 7, further comprising a solvent.

12. The resin composition according to claim 1, 2 or 7, which is used for underfill.

13. A film obtained from the resin composition according to claim 1, 2 or 7.

14. A film obtained from the resin composition according to claim 11.

15. A semiconductor device having a substrate, an IC chip electrically connected via electrodes on the substrate, and an underfill filling the space between the substrate and the IC chip, wherein the underfill is a cured product of the resin composition according to claim 12.

16. An LED display device having a substrate, an LED chip electrically connected via electrodes on the substrate, and an underfill filling the space between the substrate and the LED chip, wherein the underfill is a cured product of the resin composition according to claim 12.

17. A polymer having a repeating unit structure represented by the following formula (A):

18. A film obtained from the polymer of claim 17.

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