Resin composition, resin film, laminate, method for producing laminate, printed wiring board, and semiconductor package

Abstract

This resin composition comprises a thermosetting resin and an acrylic polymer.

Description

Resin composition method, resin film, laminate, method for manufacturing laminate, printed circuit board, and semiconductor package

[0001] This disclosure relates to resin compositions, resin films, laminates, methods for manufacturing laminates, printed circuit boards, and semiconductor packages.

[0002] In recent years, the use of glass substrates (glass substrates) as substrates for printed circuit boards has been considered. When using glass substrates as substrates for printed circuit boards, a crucial issue is how to ensure adhesion between the glass substrate and the conductive circuits formed on its surface. As a measure to improve the adhesion between the glass substrate and the conductive circuits, Patent Document 1 proposes providing a resin layer on the surface of the glass substrate to assist in adhesion to the conductors.

[0003] International Publication No. 2013 / 150940

[0004] Existing resin compositions developed for bonding substrates and conductors have room for improvement in terms of the durability of their adhesive strength to conductors. In view of the above circumstances, embodiments of this disclosure aim to provide a resin composition with excellent durability in adhesive strength to conductors, a resin film using this resin composition, a laminate, a method for manufacturing the laminate, a printed circuit board, and a semiconductor package.

[0005] The following embodiments are included as means for solving the above problems: <1> A resin composition comprising a thermosetting resin and an acrylic polymer. <2> The resin composition according to <1>, wherein the weight-average molecular weight of the acrylic polymer is 50,000 to 1,500,000. <3> The resin composition according to <1> or <2>, wherein the glass transition temperature of the acrylic polymer is 30°C or less. <4> The resin composition according to any one of <1> to <3>, wherein the acrylic polymer has a functional group that can react with the thermosetting resin. <5> The resin composition according to any one of <1> to <4>, wherein the content of the acrylic polymer is 10% to 60% by mass relative to the total solid content of the resin composition. <6> The resin composition according to any one of <1> to <5>, wherein the thermosetting resin comprises an epoxy resin. <7> The resin composition according to any one of <1> to <6>, wherein the thermosetting resin comprises an epoxy resin and an ester curing agent. <8> The resin composition according to <7>, wherein the curing agent comprises an ester curing agent. <9> The resin composition according to any one of <1> to <8>, further comprising a coupling agent. <10> The resin composition according to <9>, wherein the coupling agent has a functional group that can react with the thermosetting resin. <11> The resin composition according to any one of <1> to <10> for bonding a substrate and a conductor or insulator. <12> The resin composition according to <11>, wherein the substrate is a glass substrate. <13> A resin film comprising the resin composition according to any one of <1> to <12>. <14> A laminate comprising a substrate, a conductor or insulator, and a cured product of the resin composition according to any one of <1> to <12> disposed between the substrate and the conductor or insulator. <15> A method for manufacturing a laminate having a substrate, a conductor or insulator, and a cured product of a resin composition disposed between the substrate and the conductor or insulator, comprising: applying a resin composition according to any one of <1> to <12> or a resin film according to <13> to the surface of the substrate; curing the resin composition or the resin film to obtain a cured product; and arranging the conductor or insulator on the surface of the cured product. <16> A printed wiring board comprising the laminate according to <14>.A semiconductor package comprising a printed circuit board as described in <17> and <16>, and a semiconductor element.

[0006] This disclosure provides a resin composition having excellent durability in adhesive strength to conductors or insulators, a resin film using this resin composition, a laminate, a method for manufacturing the laminate, a printed circuit board, and a semiconductor package.

[0007] In this disclosure, numerical ranges indicated using "~" include the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages in this disclosure, the upper or lower limit of one numerical range may be replaced by the upper or lower limit of another numerical range described in stages. Also, in numerical ranges described in this disclosure, the upper or lower limit of that range may be replaced by the values ​​shown in the examples. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. In this disclosure, the term "layer" includes cases where the layer is formed over the entire region when the region in which the layer exists is observed, as well as cases where the layer is formed over only a part of the region.

[0008] In this disclosure, "solids" refers to components other than volatile components such as solvents. Components that do not volatilize even if they are in a liquid state and remain in the cured product are considered to be solids.

[0009] In this disclosure, "semi-cured product" is synonymous with a resin composition in the B-stage state as defined in JIS K 6800 (2006), and "cured product" is synonymous with a resin composition in the C-stage state as defined in JIS K 6800 (2006).

[0010] The mechanisms of action described in this disclosure are speculative and do not limit the mechanisms by which the effects of this disclosure are achieved. Furthermore, embodiments that arbitrarily combine the matters described in this disclosure are also included in this embodiment.

[0011] [Resin Composition] The resin composition of this disclosure is a resin composition comprising a thermosetting resin and an acrylic polymer.

[0012] As shown in the examples described later, the resin composition of this disclosure, which includes a thermosetting resin and an acrylic polymer, exhibits superior adhesion to conductors or insulators and superior durability compared to resin compositions that include a thermosetting resin but do not include an acrylic polymer. The reason for this is thought to be, for example, as follows: The substrate to which the resin composition is bonded and the conductor or insulator generally have different coefficients of thermal expansion. Therefore, in environments with repeated temperature fluctuations, the adhesive strength of the resin composition may decrease due to stress caused by the difference in the coefficients of thermal expansion between the substrate and the conductor or insulator. The resin composition of this disclosure includes an acrylic polymer in addition to the thermosetting resin. Therefore, the cured product of the resin composition of this disclosure exhibits an effect that relieves stress caused by the difference in the coefficients of thermal expansion between the substrate and the conductor or insulator, thereby suppressing a decrease in adhesive strength to the conductor or insulator. The components contained in the resin composition of this disclosure will be described below.

[0013] (Thermosetting Resin) The resin composition of this disclosure includes a thermosetting resin. In this disclosure, "thermosetting resin" means a compound that forms a three-dimensional crosslinked structure and a cured product upon heating. The thermosetting resin may cure by self-polymerization or by reaction with a curing agent, crosslinking agent, etc. The resin composition of this disclosure may contain only one type of thermosetting resin or two or more types.

[0014] Examples of thermosetting resins include epoxy resins, cyanate resins, maleimide compounds, bismaleimides, addition polymers of bismaleimides and diamines, phenolic resins, polyphenylene ether resins, bismaleimide resins, resol resins, benzoxazine resins, oxetane resins, isocyanate resins, amino resins, unsaturated polyester resins, isocyanate resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins. From the viewpoint of heat resistance, mechanical strength, and adhesive strength of the cured product, it is preferable that the resin composition contains epoxy resin as the thermosetting resin.

[0015] The type of epoxy resin is not particularly limited and can be selected according to the application of the resin composition. Epoxy resins are classified into glycidyl ether type, glycidyl amine type, glycidyl ester type, etc. Among these, glycidyl ether type epoxy resins are preferred. From a molecular structure perspective, examples of epoxy resins include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy resin; alicyclic epoxy resins such as dicyclopentadiene-type epoxy resin; aliphatic chain epoxy resins; novolac-type epoxy resins such as phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, bisphenol A novolac-type epoxy resin, bisphenol F novolac-type epoxy resin, phenol aralkyl novolac-type epoxy resin, and biphenyl aralkyl novolac-type epoxy resin; stilbene-type epoxy resin; naphthalene-backbone-containing epoxy resins such as naphthol novolac-type epoxy resin and naphthol aralkyl-type epoxy resin; biphenyl aralkyl-type epoxy resin; xylylene-type epoxy resin; and dihydroanthracene-type epoxy resin.

[0016] From the viewpoint of heat resistance and mechanical strength of the cured product, the resin composition preferably contains an epoxy resin having biphenyl-diyl groups. In this disclosure, "biphenyl-diyl group" means a divalent group obtained by removing two hydrogen atoms from the hydrogen atoms directly bonded to the two aromatic rings constituting biphenyl. The two aromatic rings constituting biphenyl may or may not have substituents. Specific examples of biphenyl-diyl groups include biphenyl-2,3'-diyl group, biphenyl-2,4'-diyl group, biphenyl-3,4'-diyl group, and biphenyl-4,4'-diyl group. Among these, biphenyl-4,4'-diyl group is preferred. The epoxy resin having biphenyl-diyl groups may be a compound having one or more biphenyl-diyl groups and two or more epoxy groups in its molecule.

[0017] Examples of the epoxy resin having a biphenyldiyl group include biphenyl aralkyl type epoxy resins and biphenyl type epoxy resins such as biphenol diglycidyl ether and tetramethylbiphenol diglycidyl ether. Among these, from the viewpoint of adhesion to a conductor or an insulator, biphenyl aralkyl type epoxy resins are preferable.

[0018] The biphenyl aralkyl type epoxy resin may be a compound containing a structure represented by the following general formula (A-1).

[0019]

[0020] (In the formula, R Ａ１ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and n Ａ１ is an integer of 0 to 3.)

[0021] Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R Ａ１ in the above general formula (A-1) include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and n-pentyl group; alkenyl groups having 2 to 5 carbon atoms; alkynyl groups having 2 to 5 carbon atoms and the like. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom and the like. N Ａ１ in the above general formula (A-1) may be an integer of 0 to 2, or may be 0. When n Ａ１ is an integer of 2 or more, a plurality of R Ａ１ may be the same as or different from each other.

[0022] The epoxy resin containing the structure represented by the above general formula (A-1) may be an epoxy resin represented by the following general formula (A-2).

[0023]

[0024] (In the formula, R Ａ１ and n Ａ１ are the same as those in the above general formula (A-1), and n Ａ２ is an integer of 1 to 10.)

[0025] In the above general formula (A-2), a plurality of Rs Ａ１ or a plurality of ns Ａ１ may be the same as or different from each other. In the above general formula (A-2), n Ａ２ may be an integer of 1 to 10, may be an integer of 1 to 7, or may be an integer of 1 to 5.

[0026] From the viewpoint of imparting appropriate flexibility to the cured product, the resin composition of the present disclosure may contain an epoxy resin having an alkylene group having 3 or more carbon atoms as the epoxy resin.

[0027] The epoxy resin having an alkylene group having 3 or more carbon atoms may be an epoxy resin having an alkylene group having 3 or more carbon atoms and having 2 or more epoxy groups. The number of carbon atoms of the alkylene group having 3 or more carbon atoms in the epoxy resin having an alkylene group having 3 or more carbon atoms may be 3 to 10, may be 4 to 9, or may be 5 to 8 from the viewpoints of adhesiveness and heat resistance to a conductor or an insulator.

[0028] The alkylene group having 3 or more carbon atoms in the epoxy resin having an alkylene group having 3 or more carbon atoms may be a group derived from an alkylene glycol having 3 or more carbon atoms. Examples of the alkylene glycol having 3 or more carbon atoms include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and the like. The epoxy resin having an alkylene group having 3 or more carbon atoms may be an aliphatic epoxy resin in which two glycidyl ether groups are bonded to the alkylene group having 3 or more carbon atoms, or an aromatic epoxy resin in which two glycidyl ether groups are bonded to an aromatic ring.

[0029] Examples of the epoxy resin having an alkylene group having 3 or more carbon atoms include a compound represented by the following general formula (C-1) and a compound represented by the following general formula (C-2).

[0030]

[0031] (In the formula, X ＣEach of these is a residue obtained by removing two phenolic hydroxyl groups from a polyfunctional phenol compound, Y Ｃ This is a residue obtained by removing two hydroxyl groups from an alkylene glycol having 3 or more carbon atoms, n Ｃ１ n is an integer between 1 and 5. Ｃ２ (This is an integer between 1 and 5.)

[0032]

[0033] (In the formula, Y Ｃ This is a residue obtained by removing two hydroxyl groups from an alkylene glycol having 3 or more carbon atoms, n Ｃ３ (This is an integer between 1 and 15.)

[0034] Examples of the above-mentioned polyfunctional phenol compounds include bisphenol resins such as bisphenol A, bisphenol F, and bisphenol S; novolac resins such as phenol novolac, cresol novolac, bisphenol novolac, and bisphenol F novolac; and catechol and dihydroxynaphthalene.

[0035] The functional group equivalent of a thermosetting resin (epoxy equivalent in the case of epoxy resin) may be 50 g / eq to 5,000 g / eq, 70 g / eq to 3,000 g / eq, 80 g / eq to 2,000 g / eq, 100 g / eq to 1,000 g / eq, 150 g / eq to 700 g / eq, or 200 g / eq to 600 g / eq, from the viewpoint of adhesion to conductors or insulators. The functional group equivalent of a thermosetting resin can be measured according to the method specified in JIS K 0070:1992.

[0036] The epoxy equivalent of the epoxy resin having a biphenyl-diyl group may be 150 g / eq to 400 g / eq, 200 g / eq to 350 g / eq, or 270 g / eq to 320 g / eq, from the viewpoint of adhesion to conductors or insulators.

[0037] The epoxy equivalent of the epoxy resin having an alkylene group with 3 or more carbon atoms may be 250 g / eq to 900 g / eq, 300 g / eq to 600 g / eq, or 350 g / eq to 550 g / eq, from the viewpoint of adhesion to conductors or insulators.

[0038] When the thermosetting resin contains an epoxy resin having biphenyl-diyl groups and an epoxy resin having alkylene groups with 3 or more carbon atoms, the mass ratio (epoxy resin having biphenyl-diyl groups: epoxy resin having alkylene groups with 3 or more carbon atoms) is not particularly limited. For example, it may be selected from the range of 1:0.25 to 1:3.

[0039] The epoxy resin content in the resin composition of this disclosure is preferably 10% to 80% by mass, more preferably 15% to 75% by mass, even more preferably 20% to 70% by mass, and particularly preferably 25% to 65% by mass, based on the total amount of resin components in the resin composition of this embodiment. In this disclosure, "resin components in the resin composition" means the sum of thermosetting resin and acrylic polymer.

[0040] The resin composition of this disclosure may include a curing agent as a thermosetting resin. For example, the resin composition may include an epoxy resin as a thermosetting resin and a curing agent for the epoxy resin.

[0041] Examples of curing agents for epoxy resins include ester curing agents, phenol curing agents, amine curing agents, acid anhydride curing agents, polymer captan curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents, benzoxazine curing agents, and carbodiimide curing agents.

[0042] Ester curing agents are preferred as curing agents for epoxy resins. Ester curing agents refer to compounds having one or more ester groups that can react with epoxy groups, and are sometimes called active ester curing agents.

[0043] When a phenol curing agent or amine curing agent is used as a curing agent for epoxy resin, secondary hydroxyl groups are generated as the epoxy ring opens. In contrast, when an ester curing agent is used as a curing agent for epoxy resin, secondary hydroxyl groups are not generated, and a cured product with a low dielectric constant can be obtained. Furthermore, when the surface of the cured product formed by the reaction of epoxy resin and ester curing agent is subjected to modification treatments such as ultraviolet irradiation, ozone treatment, or plasma treatment, oxygen-containing groups are generated on the surface of the cured product due to molecular cleavage. These oxygen-containing groups act to enhance the adhesion to conductors or insulators.

[0044] Examples of ester curing agents include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and ester compounds of heterocyclic hydroxy compounds. Among these, phenol ester compounds are preferred.

[0045] The ester curing agent is preferably a compound having two or more ester groups in one molecule, and more preferably a compound having two or more ester groups in one molecule, wherein the two or more ester groups are formed from a polycarboxylic acid compound and a compound having a phenolic hydroxyl group. The ester group formed from a polycarboxylic acid compound and a compound having a phenolic hydroxyl group is an ester group formed by an esterification reaction (condensation reaction) between the carboxyl group of the polycarboxylic acid compound and the phenolic hydroxyl group of the compound having a phenolic hydroxyl group.

[0046] Examples of polycarboxylic acid compounds include compounds having two or more aliphatic carboxyl groups and compounds having two or more aromatic carboxyl groups. Examples of compounds having two or more aliphatic carboxyl groups include succinic acid, maleic acid, and itaconic acid. Examples of compounds having two or more aromatic carboxyl groups include benzenedicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; benzenetricarboxylic acids such as trimesic acid; and benzenetetracarboxylic acids such as pyromellitic acid. Among these, from the viewpoint of heat resistance and dielectric properties, compounds having two or more aromatic carboxyl groups may be used, or benzenedicarboxylic acids may be used. Polycarboxylic acid compounds may be used individually or in combination of two or more.

[0047] Compounds having phenolic hydroxyl groups include compounds having one phenolic hydroxyl group, compounds having two phenolic hydroxyl groups, and compounds having three or more phenolic hydroxyl groups. Compounds having one phenolic hydroxyl group include monophenol compounds such as phenol, o-cresol, m-cresol, and p-cresol; mononaphthol compounds such as α-naphthol and β-naphthol; and hydroxybenzophenone. Compounds having two phenolic hydroxyl groups include dihydroxybenzene compounds such as hydroquinone, resorcinol, and catechol; bisphenol compounds such as bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, and methylated bisphenol S; dihydroxynaphthalene compounds such as 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene; and phenolphthalein and dicyclopentadiene-type phenolic resins having two phenolic hydroxyl groups. Compounds having three or more phenolic hydroxyl groups include trihydroxybenzophenone, benzenetriol, tetrahydroxybenzophenone, phenol novolac resin, and phenol aralkyl resin. A single compound with phenolic hydroxyl groups may be used, or two or more may be used in combination.

[0048] The ester curing agent having an ester group formed from a polycarboxylic acid compound and a compound having a phenolic hydroxyl group may be a compound represented by the following general formula (B-1).

[0049]

[0050] (In the formula, X Ｂ These are, independently, residues of a polycarboxylic acid compound with two carboxyl groups removed, Y Ｂ These are residues that, independently, remove two phenolic hydroxyl groups from a compound that has two phenolic hydroxyl groups. Ｂ Each of these is independently a residue from which one phenolic hydroxyl group has been removed from a compound having one or two phenolic hydroxyl groups. Ｂ１ (This is an integer between 0 and 10.)

[0051] n in the above general formula (B-1) Ｂ１ This can be an integer between 0 and 5, an integer between 0 and 4, or an integer between 0 and 3.

[0052] The functional group equivalent of the curing agent (ester equivalent in the case of an ester curing agent) may be 100 g / eq to 1000 g / eq, 100 g / eq to 300 g / eq, 150 g / eq to 270 g / eq, or 200 g / eq to 250 g / eq, from the viewpoint of adhesion to conductors or insulators. The functional group equivalent of the curing agent can be measured according to the method specified in JIS K 0070:1992.

[0053] The content of the curing agent in the resin composition of this disclosure is preferably 5% to 80% by mass, more preferably 10% to 60% by mass, and even more preferably 15% to 50% by mass, based on the total amount of resin components in the resin composition. When the content of the ester curing agent is within the above range, the curability and adhesion to conductors or insulators tend to be superior.

[0054] The content of thermosetting resin in the resin composition is not particularly limited. From the viewpoint of the curing reactivity of the resin composition, the content of thermosetting resin is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 45% by mass or more, based on the total solid content of the resin composition. From the viewpoint of the durability of adhesion to conductors or insulators, the content of thermosetting resin is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less, based on the total solid content of the resin composition. In this disclosure, if the acrylic polymer contained in the resin composition has epoxy groups, the content of the acrylic polymer having epoxy groups is not included in the content of thermosetting resin as described above.

[0055] When the resin composition includes an epoxy resin as a thermosetting resin and a curing agent for the epoxy resin, the mass ratio of the epoxy resin to the curing agent is not particularly limited. For example, the mass ratio of the epoxy resin to the curing agent may be set so that the equivalent ratio [epoxy groups / functional groups] of epoxy groups derived from the epoxy resin and functional groups derived from the curing agent is a desired value. From the viewpoint of curing reactivity and adhesion to conductors or insulators, the above equivalent ratio is preferably 0.5 to 2.0, more preferably 0.75 to 1.75, and even more preferably 1.0 to 1.5.

[0056] (Acrylic Polymer) The resin composition of this disclosure contains an acrylic polymer. In this disclosure, "acrylic polymer" means a polymer of monomers having an ethylenically unsaturated group, wherein 50% by mass or more of the total monomers are compounds having a (meth)acryloyl group. In this disclosure, "compound having a (meth)acryloyl group" means a compound having an acryloyl group or a methacryloyl group. In addition to compounds having a (meth)acryloyl group, the acrylic polymer may also contain compounds that do not fall under the category of compounds having a (meth)acryloyl group, such as styrene and vinyl acetate, as polymerization components. The acrylic polymer contained in the resin composition may be one type or two or more types. The polymerization components of the acrylic polymer may be one type or two or more types.

[0057] From the viewpoint of increasing adhesion to conductors or insulators, the polymerization component of the acrylic polymer preferably contains a (meth)acrylic acid ester, and more preferably contains a (meth)acrylic acid ester represented by the following general formula (D-1).

[0058]

[0059] In the formula, R Ａ１ R represents a hydrogen atom or a methyl group. Ａ２ R represents a monovalent hydrocarbon group. Ａ２ The monovalent hydrocarbon group represented by may or may not have substituents.

[0060] R Ａ２ Examples of monovalent hydrocarbon groups represented by R include alkyl groups, aryl groups, and aralkyl groups. Ａ２ The number of carbon atoms in the alkyl group represented by is preferably 1 to 20, more preferably 1 to 15, and even more preferably 2 to 10. Examples of alkyl groups include methyl, ethyl, propyl, butyl, 2-ethylhexyl, cycloalkyl groups, and cycloalkyl-substituted alkyl groups. Examples of cycloalkyl groups include cyclohexyl, norbornyl, tricyclodecanyl, isobornyl, and adamantyl groups. Ａ２ The number of carbon atoms in the aryl group represented by is preferably 6 to 13, and more preferably 6 to 10. Examples of aryl groups include phenyl groups and nonylphenyl groups. Ａ２ The number of carbon atoms in the aralkyl group represented by is preferably 7 to 15, and more preferably 7 to 11. Examples of aralkyl groups include benzyl groups and 4-methylbenzyl groups. Ａ２ When the monovalent hydrocarbon group represented by has substituents, examples of substituents include hydroxyl groups, halogen atoms, oxygen-containing hydrocarbon groups, nitrogen-containing cyclic groups, and the like.

[0061] Specific examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobutyl (meth)acrylate, ethylene glycol methyl ether (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.0(2,6)]deca-8-yl (meth)acrylate, isodecyl (meth)acrylate, octadecyl (meth)acrylate, lauryl (meth)acrylate, allyl (meth)acrylate, norbornyl methyl (meth)acrylate, tricyclodecylethyl (meth)acrylate, phenyl (meth)acrylate, nonylphenyl (meth)acrylate, benzyl (meth)acrylate, 4-methylbenzyl (meth)acrylate, and the like.

[0062] The polymerization components of the acrylic polymer may include monomers having functional groups that can react with thermosetting resins (hereinafter also referred to as reactive functional groups). Examples of reactive functional groups include carboxyl groups, epoxy groups (glycidyl groups), hydroxyl groups, amino groups, amide groups, nitrile groups, acid anhydride groups, and vinyl groups. Among these, epoxy groups are preferred from the viewpoint of low hygroscopicity and solder heat resistance.

[0063] Examples of monomers having reactive functional groups include monomers having carboxyl groups such as acrylic acid and methacrylic acid; monomers having epoxy groups such as glycidyl acrylate and glycidyl methacrylate; monomers having hydroxyl groups such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; monomers having amino groups such as dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate; monomers having amide groups such as acrylamide, methacrylamide, dimethylacrylamide, and dimethylmethacrylamide; monomers having nitrile groups such as acrylonitrile; and monomers having substituents containing acid anhydride groups such as trimellitic anhydride (meth)acryloyloxyethyl ester and cyclohexanetricarboxylic acid anhydride (meth)acryloyloxyethyl ester.

[0064] The polymerization components of the acrylic polymer may include monomers other than those mentioned above. Examples of other monomers include (meth)acrylic acid N-vinylpyrrolidone, N-(meth)acryloylmorpholine, aromatic vinyl compounds such as styrene, vinyl acetate, and N-substituted maleimide compounds.

[0065] From the viewpoint of improving the durability of adhesion to conductors or insulators, it is preferable that the proportion of (meth)acrylic acid ester in the polymerization component of the acrylic polymer be 70% by mass or more, 80% by mass or more, or 90% by mass or more. The proportion of (meth)acrylic acid ester in the polymerization component of the acrylic polymer may be 100% by mass or less, 99.5% by mass or less, or 97% by mass or less.

[0066] The weight-average molecular weight (Mw) of the acrylic polymer contained in the resin composition is not particularly limited. From the viewpoint of durability of adhesive strength to conductors or insulators, it is preferable that the weight-average molecular weight of the acrylic polymer is 50,000 to 1,500,000 or 100,000 to 1,500,000.

[0067] In this disclosure, the weight-average molecular weight of the acrylic polymer is measured in polystyrene equivalent by gel permeation chromatography (GPC). The GPC measurement conditions are as follows. Instrument: High-speed GPC instrument HLC-8320GPC Detector: UV absorbance detector UV-8320 [Tosoh Corporation] Column: Guard column; TSK Guardcolumn SuperHZ-L + Column; TSKgel SuperHZM-N + TSKgel SuperHZM-M + TSKgel SuperH-RC (all manufactured by Tosoh Corporation, product names) Column size: 4.6 × 20 mm (guard column), 4.6 × 150 mm (column), 6.0 × 150 mm (reference column) Eluent: Tetrahydrofuran Sample concentration: 10 mg / 5 mL Injection volume: 25 μL Flow rate: 1.00 mL / min Measurement temperature: 40°C Calibration curve: Standard polystyrene: TSKstandard The equation is approximated using a cubic equation with POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) (manufactured by Tosoh Corporation, product name).

[0068] The glass transition temperature (Tg) of the acrylic polymer is not particularly limited. From the viewpoint of durability of adhesive strength to conductors or insulators, the Tg of the acrylic polymer is preferably 30°C or lower, more preferably 20°C or lower, even more preferably 10°C or lower, and particularly preferably 5°C or lower. From the viewpoint of balancing the properties of the cured product, the Tg of the acrylic polymer is preferably -20°C or higher, more preferably -10°C or higher, and even more preferably -5°C or higher. In this disclosure, the Tg of the acrylic polymer is the value measured using a differential scanning calorimetry (DSC). Specifically, the Tg is measured using a differential scanning calorimetry (DSC) under conditions of a nitrogen atmosphere, a sample of 10 mg, and a heating rate of 10°C / min, and the inflection point of the obtained DSC curve is defined as the Tg of the acrylic polymer.

[0069] The Tg of an acrylic polymer can be adjusted by the combination of monomers used as polymerization components. For example, the Tg of an acrylic polymer can be lowered by increasing the proportion of monomers with relatively low Tg (e.g., Tg of 30°C or less) in the polymerization components. In this disclosure, the Tg of a monomer refers to the Tg of a polymer obtained solely from that monomer. Specific examples of monomers with a Tg of 30°C or less include ethyl acrylate (-22°C), n-butyl acrylate (-54°C), n-butyl methacrylate (20°C), 2-ethylhexyl acrylate (-70°C), 2-ethylhexyl methacrylate (-10°C), n-octyl acrylate (-65°C), lauryl acrylate (-3°C), lauryl methacrylate (-65°C), benzyl acrylate (6°C), phenoxyethyl acrylate (-22°C), 2-methoxyethyl acrylate (-50°C), 2-hydroxyethyl acrylate (-15°C), 4-hydroxybutyl acrylate (-80°C), dimethylaminoethyl methacrylate (18°C), vinyl acetate (30°C), and the like.

[0070] The acrylic polymer may have reactive functional groups. When the resin composition contains an acrylic polymer with reactive functional groups, the durability of the adhesive strength of the cured product to conductors or insulators tends to be superior. The acrylic polymer may also have reactive functional groups in its side chains.

[0071] Acrylic polymers having reactive functional groups can be obtained, for example, by polymerizing a polymerization component containing a monomer having a reactive functional group. When the resin composition contains an epoxy resin as a thermosetting resin, the reactive functional group is preferably an epoxy group (glycidyl group), an amino group, a carboxyl group, a hydroxyl group, an acid anhydride group, or an amide group, with the epoxy group being more preferred.

[0072] The functional group equivalent (epoxy equivalent in the case of epoxy groups) of an acrylic polymer having a functional group that can react with a thermosetting resin is not particularly limited. For example, it may be selected from the range of 250 g / eq to 20,000 g / eq. In this disclosure, the functional group equivalent of the acrylic polymer can be measured according to the method specified in JIS K 0070:1992.

[0073] The content of acrylic polymer in the resin composition is not particularly limited. From the viewpoint of the durability of adhesion to conductors or insulators, the content of acrylic polymer is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, based on the total solid content of the resin composition. From the viewpoint of the curing reactivity of the resin composition, the content of acrylic polymer is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition.

[0074] (Curing Accelerator) The resin composition of this disclosure may contain a curing accelerator. When the resin composition of this disclosure contains a curing accelerator, the curing reactivity is improved, and the dielectric properties, heat resistance, and adhesion to conductors or insulators of the cured product tend to be better. The curing accelerator contained in the resin composition may be one type or two or more types.

[0075] Examples of curing accelerators include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, tributylamine, pyridine, and dicyandiamide; imidazole compounds such as methylimidazole, phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitate; isocyanate-masquimidazole compounds such as the addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine and quaternary phosphonium compounds which are the addition reaction products of p-benzoquinone and tri-n-butylphosphine; Examples include organic peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyn-3, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, and α,α'-bis(t-butylperoxy)diisopropylbenzene; inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2'-dimethylvaleronitrile); carboxylates of manganese, cobalt, zinc, etc.; and acidic catalysts such as p-toluenesulfonic acid. Among these, imidazole compounds and phosphorus compounds are preferred.

[0076] If the resin composition of this disclosure contains a curing accelerator, the content of the curing accelerator is not particularly limited. From the viewpoint of the curing reactivity of the resin composition, the content of the curing accelerator may be 0.01 to 10 parts by mass, 0.1 to 7 parts by mass, or 0.5 to 5 parts by mass per 100 parts by mass of the thermosetting resin.

[0077] (Coupling Agent) The resin composition of this disclosure may contain a coupling agent. When the resin composition of this disclosure contains a coupling agent, the adhesion of the cured product to a conductor or insulator tends to be better. Examples of coupling agents include silane coupling agents, aluminate coupling agents, titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds. Among these, silane coupling agents are preferred.

[0078] Specifically, silane coupling agents include: silane compounds having an amino group such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane; silane compounds having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane; silane compounds having an epoxy group such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; and silane compounds having a styryl (vinylphenyl) group such as p-styryltrimethoxysilane. Examples include silane compounds having a methacryloyl group, such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; silane compounds having an acryloyl group, such as 3-acryloxypropyltrimethoxysilane; silane compounds having a ureido group, such as 3-ureidopropyltrialkoxysilane; silane compounds having an isocyanate group, such as 3-isocyanatetopropyltriethoxysilane; and silane compounds having a mercapto group, such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.

[0079] The coupling agent may have functional groups that can react with the thermosetting resin. When the resin composition contains a coupling agent that has functional groups that can react with the thermosetting resin, the durability of the adhesive strength of the cured product to conductors or insulators tends to be superior.

[0080] When a coupling agent has a functional group that can react with a thermosetting resin, the type of functional group is not particularly limited and can be selected according to the type of thermosetting resin. When the resin composition includes an epoxy resin as the thermosetting resin, examples of functional groups that can react with the thermosetting resin include epoxy groups, amino groups, and other functional groups containing active hydrogen, with amino groups being preferred.

[0081] If the resin composition of this disclosure contains a coupling agent, the content of the coupling agent is not particularly limited. From the viewpoint of adhesion of the cured product to a conductor or insulator, the content of the coupling agent may be 0.01 to 5 parts by mass, 0.05 to 2 parts by mass, or 0.1 to 1 part by mass per 100 parts by mass of the total amount of resin components in the resin composition.

[0082] (Other Components) The resin compositions of this disclosure may, as necessary, contain components other than thermosetting resins, acrylic polymers, curing accelerators, and coupling agents (also referred to as other components). Specific examples of other components include inorganic fillers, polymer resin particles, flame retardants, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, organic solvents, ion trapping materials, leveling agents, and the like. The content of the above-mentioned components in the resin compositions of this disclosure is not particularly limited and can be used as necessary, within a range that does not impair the effects of this disclosure. The resin compositions of this disclosure may not contain the above-mentioned optional components, depending on the desired performance.

[0083] Examples of inorganic fillers include silica, alumina, titanium oxide, mica, beryllium, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, and silicon carbide.

[0084] Examples of polymer resin particles include acrylic resin particles, urethane microparticles, silicone microparticles, methacrylate-butadiene-styrene microparticles, acrylic-silicone microparticles, polyamide microparticles, and polyimide microparticles. The polymer resin particles may have a uniform structure or a core-shell structure.

[0085] (Organic solvents) The resin compositions of this disclosure may contain organic solvents from the viewpoint of handling. Examples of organic solvents include alcoholic solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethyl sulfoxide; and ester solvents such as γ-butyrolactone.

[0086] If the resin composition of this disclosure contains an organic solvent, the content of the organic solvent is not particularly limited and can be set according to the form of use of the resin composition, the desired viscosity of the resin composition, etc.

[0087] The resin composition of this disclosure can be manufactured by mixing each component in a known manner. In this process, each component may be dissolved or dispersed while being stirred. The mixing order, temperature, time, and other conditions are not particularly limited and may be set arbitrarily depending on the type of raw materials, etc.

[0088] The resin composition of this disclosure may be in an uncured state (A-stage) or a semi-cured state (B-stage).

[0089] The resin compositions of this disclosure exhibit excellent adhesive strength to conductors or insulators and have excellent durability, making them suitable for bonding substrates to conductors or insulators. In particular, the resin compositions of this disclosure are suitable for bonding glass substrates to conductors or insulators. The substrates and conductors or insulators bonded using the resin compositions of this disclosure may be substrates and conductors or insulators included in printed circuit boards, or substrates and conductors or insulators used in products other than printed circuit boards. The resin compositions of this disclosure are suitable, for example, for manufacturing laminates as described later.

[0090] [Resin Film] The resin film of this disclosure is a resin film containing the resin composition of this disclosure. The resin composition contained in the resin film may be in an uncured state (A-stage) or a semi-cured state (B-stage). The resin film of this disclosure is used, for example, to form a layer consisting of a cured resin film on a substrate.

[0091] The resin film of this disclosure can be manufactured, for example, by applying a varnish-like resin composition containing an organic solvent to a support and then heating and drying it. Examples of support materials include plastic films such as polyethylene terephthalate (PET) film, metal foil, and release paper. The temperature and time for heating and drying after applying the resin composition to the support material can be, for example, 50°C to 200°C and 1 minute to 30 minutes. The thickness of the resin film is not particularly limited and can be selected according to the application. The thickness of the resin film may be, for example, 0.1 μm to 50 μm, 0.5 μm to 30 μm, or 1 μm to 20 μm.

[0092] [Laminate] The laminate of the present disclosure is a laminate having a substrate, a conductor or insulator, and a cured product of the above-mentioned resin composition disposed between the substrate and the conductor or insulator.

[0093] In the laminate of this disclosure, the type of substrate is not particularly limited and includes glass substrates, glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin (bismaleimide-triazine resin) substrates, thermosetting polyphenylene ether substrates, etc. Since the resin composition of this disclosure exhibits excellent adhesion to glass substrates, glass substrates are preferred as the substrate.

[0094] In this disclosure, "glass substrate" means a substrate made solely of glass. Therefore, a substrate made of glass and a dissimilar material, such as a prepreg made by impregnating glass cloth with resin, does not qualify as a "glass substrate." Examples of materials for glass substrates include alkali-free glass, soda glass, borosilicate glass, aluminosilicate glass, and quartz glass. A glass substrate may have parts made of materials other than glass, such as wiring and through electrodes. In this case, the cured resin composition may be in contact with the parts made of materials other than glass.

[0095] The thickness of the glass substrate may be 30 μm to 2 mm, 50 μm to 1.5 mm, or 100 μm to 1 mm, from the viewpoint of mechanical strength and thinning of the printed circuit board.

[0096] The material of the conductor is not particularly limited as long as it has the desired electrical conductivity, and can be selected from copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, alloys containing at least one of these metal elements, etc. The material of the insulator is not particularly limited as long as it has the desired electrical insulation properties, and can be resin, ceramic, mixtures thereof, etc. The conductor or insulator may be formed in layers, or may have a desired pattern such as a circuit. The conductor or insulator included in the laminate of this disclosure may be a conductor only, an insulator only, or a combination of a conductor and an insulator. Examples of combinations of conductors and insulators include components used in electronic devices such as interlayer insulating films and redistribution layers.

[0097] In the laminate of the present disclosure, the substrate may have through holes. In the laminate of the present disclosure, the location where the cured resin composition is disposed between the substrate and the conductor or insulator is not particularly limited. For example, it may be the main surface of the substrate, the side surface of the substrate, or the side wall of a through hole. The laminate of the present disclosure may have areas where the cured resin composition is not disposed between the substrate and the conductor or insulator, or it may have areas where only the cured resin composition is disposed on the substrate.

[0098] From the viewpoint of achieving adhesion between the glass substrate and the conductor or insulator, it is preferable that the cured resin composition placed between the substrate and the conductor or insulator is in contact with both the substrate and the conductor or insulator, respectively. The thickness of the cured resin is not particularly limited and can be selected according to the application. The thickness of the cured resin may be, for example, 0.1 μm to 50 μm, 0.2 to 30 μm, or 0.5 μm to 20 μm.

[0099] The applications of the laminates of this disclosure are not particularly limited. For example, the laminates of this disclosure are suitably used in electronic component devices such as printed circuit boards and semiconductor packages. The number of substrates included in the laminates of this disclosure may be one or more. If the laminates of this disclosure include multiple substrates, the multiple substrates may include substrates on which cured resin compositions are not placed. In the laminates of this disclosure, the substrate on which cured resin compositions are placed may be a substrate on which through electrodes, referred to as interposers, are formed.

[0100] [Method for Manufacturing a Laminate] The method for manufacturing a laminate according to the present disclosure is a method for manufacturing a laminate having a substrate, a conductor or insulator, and a cured product of a resin composition disposed between the substrate and the conductor or insulator, comprising: applying the resin composition or resin film according to the present disclosure to the surface of the substrate (hereinafter also referred to as step 1); curing the resin composition or resin film to obtain a cured product (hereinafter also referred to as step 2); and arranging the conductor or insulator on the surface of the cured product (hereinafter also referred to as step 3).

[0101] (Step 1) In Step 1, a resin composition or resin film is applied to the surface of the substrate. Methods for applying the resin composition to the surface of the substrate include spin coating, curtain coating, slit coating, screen printing, dip coating, spray coating, etc. Methods for applying a resin film to the surface of the substrate include laminating a film-like resin film onto the substrate using a laminator or the like.

[0102] (Step 2) In Step 2, the resin composition or resin film applied to the surface of the substrate is cured to obtain a cured product. The conditions for curing the resin composition or resin film are not particularly limited and can be set according to the components of the resin composition or resin film. The heating temperature when curing the resin composition or resin film may be, for example, 120°C to 250°C, 140°C to 220°C, or 160°C to 200°C. The heating time when curing the resin composition or resin film may be, for example, 5 minutes to 180 minutes, 10 minutes to 150 minutes, or 30 minutes to 120 minutes.

[0103] (Step 3) In Step 3, a conductor or insulator is placed on the surface of the cured material. The method of placing the conductor on the surface of the cured material is not particularly limited and may be a wet method or a dry method. Specific examples of wet methods include electroless plating and electrolytic plating. Specific examples of dry methods include sputtering, vapor deposition, and ion plating. Considering the heat resistance of the cured material, it is preferable to place the conductor using a wet method. The method of placing the insulator on the surface of the cured material is not particularly limited and can be selected according to the material of the insulator. For example, if the insulator contains a thermosetting material, a method may be used in which the material before curing is applied to the surface of the cured material and then heated. The conductor or insulator may be placed in a pattern on the surface of the cured material. Patterned conductors can be formed by known methods such as subtractive plating, fully additive plating, semi-additive plating, and modified semi-additive plating. Patterned insulators can be formed by known methods such as photolithography and printing.

[0104] When the resin composition or resin film contains an epoxy resin and an ester curing agent as a thermosetting resin, at least one surface modification treatment selected from the group consisting of ultraviolet irradiation, ozone treatment, and plasma treatment may be applied to the surface of the cured product before placing a conductor or insulator on its surface. By applying a surface modification treatment to the surface of the cured product, oxygen-containing groups can be generated on the surface of the cured product, thereby further enhancing the adhesion to the conductor or insulator.

[0105] The conditions for surface modification treatment are not particularly limited and can be selected according to the components contained in the cured product. When the surface of the cured product is treated with ultraviolet irradiation, the maximum wavelength of the ultraviolet light may be, for example, in the range of 100 nm to 450 nm. The integrated amount of ultraviolet light may be, for example, 100 mJ / cm². ２ ~5,000mJ / cm ２ The range may also be . Ultraviolet light may be irradiated directly onto the cured material, or it may be irradiated through an object that transmits ultraviolet light, such as a plastic film. When plasma treatment is applied to the surface of the cured material, the plasma output may be in the range of, for example, 100W to 1,000W. The vacuum level may be, for example, 1 × 10 －４ Pa ~ 1 x 10 ２ It may also be within the range of Pa.

[0106] [Printed Wiring Boards and Semiconductor Packages] The printed wiring boards of this disclosure include the laminates of this disclosure described above. In the printed wiring boards of this disclosure, a cured product of a resin composition having excellent durability in adhesion to a conductor or insulator is disposed between the substrate and the conductor or insulator. For this reason, the printed wiring boards of this disclosure are highly reliable. The semiconductor packages of this disclosure are semiconductor packages having the laminates of this disclosure described above and semiconductor elements. The semiconductor packages of this disclosure can be manufactured, for example, by mounting semiconductor elements, memory, etc., on the printed wiring boards of this disclosure by known methods.

[0107] The embodiments of this disclosure will be specifically described below with reference to examples. However, this disclosure is not limited to the following embodiments.

[0108] (1) Preparation of the resin composition Each component listed in Table 1 was mixed with cyclohexanone as an organic solvent in the amounts listed in Table 1 at 25°C to prepare a varnish-like resin composition (solid content concentration: 65% by mass). In Table 1, the unit of the amount of each component is parts by mass (if the raw material contains a solvent, it is parts by mass on a solid content basis).

[0109] (2) Preparation of resin film The varnish-like resin composition obtained in (1) above was applied to the release layer of a PET film (manufactured by Toyobo Co., Ltd., trade name Purex A5300, thickness 50 μm) on which a release layer had been formed. Then, a resin film with a support in the B-stage state (resin film thickness 10 μm) was prepared by heating and drying at 140°C for 3 minutes.

[0110] (3) Preparation of test specimens for adhesive strength measurement. An alkali-free glass substrate (manufactured by Nippon Electric Glass Co., Ltd., product name "OA-11G", thickness 0.5 mm) was prepared as the glass substrate. The resin film with support obtained in the B-stage state in (2) above was placed on one surface of this glass substrate so that the resin film was on the glass substrate side, and the resin film was attached to one surface of the glass substrate using a vacuum laminator. Next, the support was peeled off from the resin film, and the resin film was heat-cured at 180°C for 60 minutes to form a resin cured layer. Then, using an ultraviolet irradiation device and a metal halide lamp (maximum wavelength 350-380 nm), the integrated light amount was 3,000 mJ / cm². ２A surface treatment was performed by irradiating the resin cured layer with ultraviolet light to achieve the desired result. The surface of the surface-treated resin cured layer was then treated with a sweeper solution, "Sweeping Dip Securigant P" (manufactured by Atotec Japan Co., Ltd.), at 70°C for 5 minutes. Next, it was treated with a conditioner solution, "Cleaner Securigant MVPF" (manufactured by Atotec Japan Co., Ltd.), at 60°C for 4 minutes. Next, it was treated with a pre-dip solution, "Pre-dip Neo-Gant B" (manufactured by Atotec Japan Co., Ltd.), at 25°C for 3 minutes. Next, it was treated with an activator solution, "Activator Neo-Gant 834 Concentrate" (manufactured by Atotec Japan Co., Ltd.), at 35°C for 5 minutes. Next, it was treated with an acid treatment solution, "8% by mass hydrochloric acid," at 35°C for 2 minutes. Next, it was treated with a reducer solution, "Reducer Accelerator" (manufactured by Atotec Japan Co., Ltd.), at 30°C for 7 minutes. Next, electroless plating was performed at 35°C for 20 minutes using the electroless plating solution "Basic Prigant MV TP1" (manufactured by Atotec Japan Co., Ltd.). Subsequently, electroplating was performed at 24°C and 2 A / dm using the electroplating solution "Caparaside HL" (manufactured by Atotec Japan Co., Ltd.). ２ The process was carried out for one hour to form plated copper (conductive layer) on the resin curing layer, and a test specimen was obtained. The thickness of the plated copper was set to 20 μm.

[0111] (4) Initial measurement of adhesive strength to the conductor layer The adhesive strength of the resin cured layer to the conductor layer was measured using a test specimen. Specifically, a peelable section 5 mm wide and 100 mm long was formed on the conductor layer of the test specimen by etching. One side of the 5 mm wide peelable section was peeled off and grasped with a gripper of a small benchtop testing machine (manufactured by Shimadzu Corporation, product name "EZ-TEST"), and the load was measured when it was pulled off vertically by approximately 50 mm at room temperature (25°C). The pulling speed during peeling was set to 50 mm / min.

[0112] (5) Measurement of adhesive strength to the conductor layer (after high temperature and high humidity treatment) The test specimens prepared as described above were subjected to high temperature and high humidity treatment by being held at 130°C and 85% relative humidity for 96 hours. After that, the adhesive strength to the conductor layer (after high temperature and high humidity treatment) was measured using the same method as in (4) above.

[0113] (6) Measurement of Storage Modulus and Glass Transition Temperature The resin film with support obtained in (2) above was peeled from the support and crushed to obtain resin powder in the B-stage state. A 0.3 mm thick polytetrafluoroethylene (PTFE) sheet with an opening of 60 mm x 40 mm was placed on top of the copper foil, and the resin powder was put into the opening. Furthermore, copper foil was placed on top of that to obtain a laminate. As the copper foil, a low-profile copper foil with a thickness of 18 μm (manufactured by Mitsui Mining & Smelting Co., Ltd., product name "3EC-VLP-18") was used, and it was placed so that the roughened surface was on the side facing the resin powder. Subsequently, the laminate was heated and pressurized under the conditions of a temperature of 180°C, a pressure of 1.0 MPa, and a time of 60 minutes, curing the resin powder while forming it into a plate shape, and a cured resin product (thickness: 1 mm) with copper foil placed on both sides was obtained.

[0114] A 5 mm x 30 mm test specimen was obtained from a resin-cured material from which the copper foil on both sides had been removed by immersion in an etching solution. Dynamic viscoelastic analysis was performed on this test specimen using a dynamic viscoelasticity analyzer (manufactured by UBM Co., Ltd., product name "Rheogel-E4000") under the conditions of a measurement temperature range of 40°C to 350°C, a heating rate of 5°C / min, and a frequency of 10 Hz. From the analysis results, the storage modulus E' and glass transition temperature at 40°C were obtained. The glass transition temperature was defined as the temperature (°C) at which tanδ was the maximum value in the temperature-loss tangent (tanδ) curve obtained from the dynamic viscoelastic analysis.

[0115]

[0116] The details of each material shown in Table 1 are as follows: Epoxy resin 1: Biphenyl aralkyl type epoxy resin: Manufactured by Nippon Kayaku Co., Ltd., trade name "NC-3000H", epoxy equivalent: 288 g / eq Epoxy resin 2: Bifunctional aromatic epoxy resin having alkylene groups with 3 or more carbon atoms Curing agent 1: Active ester compound containing a dicyclopentadiene type diphenol structure (Manufactured by DIC Corporation, trade name "HPC-8000L-65MT", ester equivalent: 223 g / eq) Curing agent 2: Active ester curing agent containing a naphthalene structure (Manufactured by DIC Corporation, trade name "HPC-8150-62T", ester equivalent: 229 g / eq

[0117] Acrylic polymer 1: Acrylic polymer containing epoxy groups as reactive functional groups in its side chains (Mw: 350,000, epoxy equivalent: approximately 14,000 g / eq, Tg: 10°C) Acrylic polymer 2: Acrylic polymer containing epoxy groups as reactive functional groups in its side chains (Mw: 600,000 to 800,000, epoxy equivalent: approximately 3,000 g / eq, Tg: -5°C) Acrylic polymer 3: Acrylic polymer containing epoxy groups as reactive functional groups in its side chains (Mw: 800,000 to 1,100,000, epoxy equivalent: approximately 700 g / eq, Tg: 5°C) Acrylic polymer 4: Acrylic polymer containing hydroxyl groups as reactive functional groups in its side chains (Mw: 1,200,000, hydroxyl value: 20 mg KOH / g, Tg: -37°C) Acrylic polymer 5: Acrylic polymer containing hydroxyl and carboxyl groups as reactive functional groups in its side chains (Mw: 900,000, acid value: 5 mg KOH / g, Tg: -13°C) Acrylic polymer 6: Acrylic polymer without reactive functional groups (Mw: approximately 130,000)

[0118] Curing accelerator 1: Imidazole-based curing accelerator (manufactured by Shikoku Chemicals Co., Ltd., product name "2PZ") Curing accelerator 2: Phosphorus-based curing accelerator Coupling agent: 3-aminopropyltriethoxysilane

[0119] As shown in Table 1, the cured products of the resin compositions of Examples 1 to 15, which contain acrylic polymer, showed little decrease in adhesive strength to the conductor after high-temperature and high-humidity treatment, and exhibited excellent durability of adhesive strength. The cured product of the resin composition of Comparative Example 1, which does not contain acrylic polymer, showed excellent adhesive strength to the conductor before high-temperature and high-humidity treatment, but the adhesive strength to the conductor decreased significantly after high-temperature and high-humidity treatment. The cured products of the resin compositions of Examples 1 to 13, in which the acrylic polymer contains reactive functional groups, showed superior adhesive strength to the conductor layer both before and after high-temperature and high-humidity treatment compared to the cured products of the resin compositions of Examples 14 to 15, in which the acrylic polymer does not contain reactive functional groups.

[0120] (7) Cross-cut test To evaluate the adhesion of the cured resin composition to the glass substrate, the following cross-cut test was performed. An alkali-free glass substrate (manufactured by Nippon Electric Glass Co., Ltd., product name "OA-11G", thickness 0.5 mm) was placed on one surface with a support attached in the B-stage state (using the resin compositions of Examples 1 to 15, thickness of the resin film portion: 30 μm) obtained by the same method as in (2) above, with the resin film facing the glass substrate. In this state, the resin film was attached to one surface of the glass substrate using a vacuum laminator. Next, the support was peeled off from the resin film, and the resin film was heated (180°C, 60 minutes) to cure it and a test piece for the cross-cut test was prepared. This test piece was subjected to a high-temperature, high-humidity treatment, held at 130°C and 85% relative humidity for 96 hours. After high-temperature and high-humidity treatment, six cuts were made at 1 mm intervals in the cured resin product of the test specimen using a utility knife. Then, six more cuts were made at 90-degree angles to these cuts, also at 1 mm intervals, to form a grid pattern (5 x 5 squares). Next, cellophane tape (manufactured by Nichiban Co., Ltd., product name "Cellotape®") was pressed onto the grid pattern, and the cellophane tape was peeled off at an angle of approximately 60 degrees. The presence or absence of delamination of the cured resin film after peeling off the cellophane tape was observed and evaluated according to the following criteria. In the following criteria, A indicates the best performance. A: No delamination of the cured resin layer. B: Delamination of the cured resin layer is less than 5%. C: Delamination of the cured resin layer is 5% or more but less than 15%. D: Delamination of the cured resin layer is 15% or more.

[0121] The cross-cut test evaluations of the test pieces using the resin films of Examples 1 to 15 were all A. These results suggest that the cured products of the resin compositions of this disclosure exhibit excellent adhesive strength even to glass substrates.

[0122] The disclosure of international application PCT / JP2024 / 041491 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. A resin composition comprising a thermosetting resin and an acrylic polymer.

2. The resin composition according to claim 1, wherein the weight-average molecular weight of the acrylic polymer is 50,000 to 1,500,000.

3. The resin composition according to claim 1, wherein the glass transition temperature of the acrylic polymer is 30°C or lower.

4. The resin composition according to claim 1, wherein the acrylic polymer has a functional group that can react with the thermosetting resin.

5. The resin composition according to claim 1, wherein the content of the acrylic polymer is 10% by mass to 80% by mass with respect to the total amount of solids in the resin composition.

6. The resin composition according to claim 1, wherein the thermosetting resin comprises an epoxy resin.

7. The resin composition according to claim 1, wherein the thermosetting resin comprises an epoxy resin and a curing agent.

8. The resin composition according to claim 7, wherein the curing agent comprises an ester curing agent.

9. The resin composition according to claim 1, further comprising a coupling agent.

10. The resin composition according to claim 9, wherein the coupling agent has a functional group that can react with the thermosetting resin.

11. The resin composition according to claim 1 for bonding a substrate to a conductor or insulator.

12. The resin composition according to claim 11, wherein the substrate is a glass substrate.

13. A resin film comprising the resin composition described in claim 1.

14. A laminate comprising a substrate, a conductor or insulator, and a cured product of the resin composition according to any one of claims 1 to 12, disposed between the substrate and the conductor or insulator.

15. A method for manufacturing a laminate having a substrate, a conductor or insulator, and a cured product of a resin composition disposed between the substrate and the conductor or insulator, comprising: applying a resin composition according to any one of claims 1 to 12 or a resin film according to claim 13 to the surface of the substrate; curing the resin composition or the resin film to obtain a cured product; and arranging the conductor or insulator on the surface of the cured product.

16. A printed circuit board comprising the laminate described in claim 14.

17. A semiconductor package comprising a printed circuit board according to claim 16 and a semiconductor element.

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