Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
  • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
  • C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
  • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes

Definitions

• the present invention relates to epoxy resins, curable resin compositions, cured products, and phenolic resins having specific structures, and is suitable for use in electrical and electronic components such as semiconductor encapsulants, printed wiring boards, build-up laminates, and optical waveguide devices, lightweight, high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and 3D printing applications.
• Epoxy resins have excellent electrical properties (dielectric constant, dielectric dissipation factor, insulation), mechanical properties, adhesive properties, and thermal properties (heat resistance, etc.), and are therefore widely used in the electrical and electronic fields, including in cast products, laminates, and IC encapsulation materials, as well as in structural materials, adhesives, paints, and other applications.
• Patent Document 1 the electrical and electronic fields have required further improvements in resin composition properties, including improved flame retardancy, moisture resistance, adhesion, and dielectric properties; higher purity; lower viscosity for higher filler (inorganic or organic) loading; and improved reactivity for shorter molding cycles.
• structural materials lightweight materials with excellent mechanical properties are required for aerospace applications and leisure and sports equipment applications.
• semiconductors have become increasingly complex, with thinner layers, stacked structures, systemized structures, and three-dimensional structures, requiring properties such as extremely high levels of heat resistance and high fluidity.
• the demand for improved heat resistance has become even more stringent.
• Non-Patent Documents 1 and 2 the rise in semiconductor operating temperatures has created a demand for extremely high heat resistance.
• operating temperatures of 175°C and even 200°C or higher are becoming necessary (Non-Patent Documents 1 and 2).
• Patent Document 2 investigates an epoxy resin composition to which a low-molecular-weight bisphenol F epoxy resin has been added.
• low-viscosity epoxy resins often have poor heat resistance, making it difficult to meet the need for high heat resistance.
• the present invention was made in light of these circumstances, and aims to provide an epoxy resin, a curable resin composition, and a phenolic resin, which is a precursor to epoxy resin, that have high fluidity and excellent heat resistance.
• each R independently represents a hydrocarbon group having 1 to 5 carbon atoms.
• the total number of carbon atoms in the R is 2 to 8.
• k is an integer of 1 to 3.
• a curing accelerator a polymerization initiator
• an epoxy resin represented by the following formula (d-1):
• the present invention makes it possible to provide epoxy resins, curable resin compositions, and cured products thereof that have high fluidity and excellent heat resistance.
• 1 shows a GPC chart of Synthesis Example 1.
• 1 shows a GPC chart of Synthesis Example 2.
• the phenolic resin of this embodiment is obtained by reacting a compound represented by the following formula (a) with a compound represented by the following formula (b).
• each R independently represents a hydrocarbon group having 1 to 5 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms. Having 6 or more carbon atoms can impair heat resistance and potentially reduce the elastic modulus of the cured product, which is undesirable from the viewpoint of causing warpage of the board when applied to a circuit board material. Without a hydrocarbon group, the cured product may be prone to water absorption, potentially causing swelling during solder reflow.
• the total number of carbon atoms in each independently present R is 2 to 8, preferably 2 to 6, and more preferably 2 to 5. If the total number of carbon atoms in R is 1, the effect of reducing water absorption may not be fully achieved.
• the total number of carbon atoms in R is preferably 2 to 8.
• Preferred compounds represented by formula (a) above have alkyl groups at the 2nd and 5th positions (or 3rd and 6th positions) relative to the phenolic hydroxyl group. By introducing hydrocarbon groups into these substitution positions, it is possible to obtain phenolic resins with narrow molecular weight distributions and epoxy resins derived therefrom. There are no particular restrictions on the compound as long as it has alkyl groups at the 2nd and 5th positions (or 3rd and 6th positions) relative to the phenolic hydroxyl group, but preferred compounds include 3-methyl-6-t-butylphenol, thymol, carvacrol, and 2,5-dimethylphenol.
• the compound represented by formula (b) above has a hydroxyl group at the ortho position of the aldehyde group, which, after being converted into phenolic resin and epoxy resin, creates steric hindrance, making it possible to achieve a high elastic modulus and low water absorption in the cured product.
• the reaction between the compound represented by formula (a) and the compound represented by formula (b) may be carried out using any known synthesis method, such as a method in which the reaction is carried out in a solvent in the presence of an acid catalyst.
• the compound of formula (a) is preferably reacted in an amount 1.1 to 8 times by mole relative to the compound of formula (b), more preferably 1.25 to 6 times by mole, and even more preferably 1.5 to 4 times by mole. If the amount is less than 1.1 times by mole, the resulting polymer becomes too high, making water washing difficult and risking a significant decrease in resin fluidity. If the amount is more than 8 times by mole, the yield per batch will be significantly reduced and waste will increase, which is undesirable.
• acid catalysts that can be used include hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid, as well as Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, and silica alumina, and acidic ion exchange resins. These may be used alone or in combination.
• the amount of catalyst used is 0.01 to 25% by mass, preferably 0.1 to 15% by mass, based on the total mass of the reaction substrates, phenols (compounds of formula (a) above) and salicylaldehyde (compounds of formula (b) above).
• solvents that can be used include water-insoluble solvents such as aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl isobutyl ketone and cyclopentanone, as well as alcoholic solvents such as methanol, ethanol, and isopropanol.
• water-insoluble solvents such as aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl isobut
• the solvent is not limited to these, and two or more solvents may be used in combination.
• an aprotic polar solvent may be used in combination with the water-insoluble solvent. Examples include dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methylpyrrolidone, and two or more of these may be used in combination.
• the reaction temperature is preferably 20 to 180°C, more preferably 40 to 160°C, and even more preferably 50 to 130°C. If the reaction temperature is too high, the methine structure of the trisphenolmethane structure may decompose, while if the reaction temperature is too low, the reaction may not proceed sufficiently.
• the acidic catalyst may be neutralized with an aqueous alkali solution or the like, followed by solvent recovery to obtain the target phenolic resin together with the neutralized salt.
• a water-insoluble organic solvent may be added to the oil layer and repeatedly washed with water until the wastewater becomes neutral, after which the solvent may be removed under heating and reduced pressure to obtain the target phenolic resin.
• the reaction solution is filtered after the reaction to remove the catalyst, and the solvent is then recovered to obtain the target phenolic resin.
• the residual monomer amount of the compound represented by formula (a) is preferably 0.01 to 10% by mass, more preferably 0.05 to 7.5% by mass, and even more preferably 0.1 to 5% by mass. The amount of this monomer affects the amount of residual low-molecular-weight epoxy resin, which in turn affects properties such as heat resistance.
• the phenolic resin obtained by reacting the compound represented by formula (a) above with the compound represented by formula (b) above contains 75 to 95 area % of the compound represented by formula (c) below, as detected by a differential refractometer in gel permeation chromatography analysis. If the content of the compound represented by formula (c) below is less than 75 area %, the phenolic resin of this embodiment, the epoxy resin made therefrom, and the curable resin composition containing them may not have sufficient fluidity. If it exceeds 95 area %, the phenolic resin of this embodiment, the epoxy resin made therefrom, and the curable resin composition containing them may not have sufficient heat resistance, and may have high crystallinity and reduced solvent solubility.
• R's each independently represent a hydrocarbon group having 1 to 5 carbon atoms.
• the total number of carbon atoms in the multiple R's is 2 to 8.
• k is an integer from 1 to 3.
• the preferred values of R and k are the same as in the above formula (a).
• the number average molecular weight (Mn) of the phenolic resin obtained by reacting the compound represented by formula (a) above with the compound represented by formula (b) above is preferably 300 to 1500, more preferably 325 to 1000, and even more preferably 350 to 800. If the number average molecular weight is below 300, there is a risk of reduced heat resistance due to residual raw materials, etc. If the number average molecular weight is above 1500, there is a risk of reduced fluidity due to increased molecular weight.
• the weight-average molecular weight (Mw) of the phenolic resin obtained by reacting the compound represented by formula (a) above with the compound represented by formula (b) above is preferably 300 to 1500, more preferably 325 to 1000, and even more preferably 350 to 800. If the weight-average molecular weight is below 300, there is a risk of reduced heat resistance due to residual raw materials, etc. If the weight-average molecular weight is above 1500, there is a risk of reduced fluidity due to increased molecular weight.
• the hydroxyl group equivalent of the phenolic resin obtained by reacting the compound represented by formula (a) above with the compound represented by formula (b) above is preferably 100 to 200 g/eq., more preferably 110 to 180 g/eq., and even more preferably 120 to 160 g/eq.
• the hydroxyl group equivalent may be calculated from the area percentage of gel permeation chromatography (GPC) analysis, or may be measured by titration.
• GPC gel permeation chromatography
• titration for example, a sample is acetylated using acetic anhydride in a pyridine solution, and after acetylation is complete, the remaining acid anhydride is decomposed with water. The amount of free acetic acid is measured by titrating the sample using a 0.5 N KOH ethanol solution in a potentiometric titrator, and the hydroxyl group equivalent can be determined from the results.
• the content of the polymer component of the compound represented by formula (c) above is preferably 1 to 25 area % as determined by gel permeation chromatography analysis (detected with a differential refractometer), and more preferably 3 to 15 area %. If it exceeds 25 area %, fluidity may decrease, and if it falls below 3 area %, solvent solubility and heat resistance may decrease.
• n is the average number of repeating units and is 1 to 20, preferably 1 to 10, and more preferably 1 to 5. If n is less than 1, there is a risk of a large amount of residual monomer, resulting in reduced heat resistance. If n is more than 20, there is a risk of insufficient fluidity being achieved. n can be determined by GPC analysis and may be calculated from the area percentage of each peak or the number average molecular weight (Mn).
• the epoxy resin of this embodiment will be described below.
• the epoxy resin of this embodiment can be obtained by reacting a phenolic resin obtained by reacting a compound represented by formula (a) with a compound represented by formula (b) above with an epihalohydrin.
• the epoxy resin can be obtained by subjecting the phenolic resin of this embodiment to an addition or ring-closing reaction with an epihalohydrin in the presence of a solvent and a catalyst.
• the amount of epihalohydrin used is typically 1.0 to 20.0 mol, preferably 1.5 to 10.0 mol, per mol of phenolic hydroxyl groups in the phenolic resin.
• alkali metal hydroxides examples include sodium hydroxide and potassium hydroxide.
• the alkali metal hydroxide may be a solid or an aqueous solution. When an aqueous solution is used, the alkali metal hydroxide may be continuously added to the reaction system while continuously distilling off water and epihalohydrin under reduced pressure or atmospheric pressure, followed by liquid separation to remove water and continuously return the epihalohydrin to the reaction system.
• the amount of alkali metal hydroxide used is typically 0.9 to 2.5 moles, preferably 0.95 to 1.5 moles, per mole of phenolic hydroxyl groups in the phenolic resin. If the amount of alkali metal hydroxide used is too small, the reaction will not proceed sufficiently. On the other hand, excessive use of more than 2.5 moles of alkali metal hydroxide per mole of phenolic hydroxyl groups in the phenolic resin will result in the production of unnecessary waste by-products.
• a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride may be added as a catalyst.
• the amount of quaternary ammonium salt used is typically 0.1 to 15 g, preferably 0.2 to 10 g, per mole of phenolic hydroxyl groups in the phenolic resin. If the amount used is too small, a sufficient reaction acceleration effect will not be obtained, while if the amount used is too large, the amount of quaternary ammonium salt remaining in the epoxy resin will increase, which may cause a deterioration in electrical reliability.
• the epoxidation reaction with the addition of alcohols such as methanol, ethanol, and isopropyl alcohol, or aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, and dioxane.
• alcohols such as methanol, ethanol, and isopropyl alcohol
• aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, and dioxane.
• the amount used is usually 2 to 50 mass% and preferably 4 to 20 mass% relative to the amount of epihalohydrin used.
• aprotic polar solvents the amount used is usually 5 to 100 mass% and preferably 10 to 80 mass% relative to the amount of epihalohydrin used.
• the reaction temperature is usually 30 to 90°C, and preferably 35 to 80°C.
• the reaction time is usually 0.5 to 100 hours, and preferably 1 to 30 hours.
• the reaction product is washed with water, or heated under reduced pressure to remove the epihalohydrin and solvent, without washing. Furthermore, to obtain an epoxy resin with a lower hydrolyzable halogen content, the recovered epoxy resin can be dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to carry out the reaction, ensuring ring closure.
• the amount of alkali metal hydroxide used is typically 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per mol of phenolic hydroxyl groups in the phenolic resin used for glycidylation.
• the reaction temperature is typically 50 to 120°C, and the reaction time is typically 0.5 to 24 hours.
• the resulting salt is removed by filtration, washing with water, or the like, and the solvent is then distilled off under reduced pressure with heating, to obtain the epoxy resin of this embodiment.
• the softening point of the epoxy resin of this embodiment is preferably 40 to 150°C, more preferably 45 to 125°C, and even more preferably 50 to 100°C. If the softening point is higher than 150°C, solvent is likely to remain when the resin is removed, easily forming voids during curing. There are also significant production issues, such as increased foaming during solvent removal. On the other hand, if the softening point is 40°C or lower, heat resistance and thermal decomposition resistance are adversely affected. Furthermore, the epoxy equivalent is preferably 150 to 300 g/eq., more preferably 160 to 275 g/eq., and even more preferably 170 to 250 g/eq.
• the ICI viscosity of the epoxy resin of this embodiment at 150°C is preferably 0.01 to 0.5 Pa ⁇ s, more preferably 0.01 to 0.4 Pa ⁇ s, and even more preferably 0.01 to 0.3 Pa ⁇ s. If the ICI viscosity at 150°C exceeds 0.5 Pa ⁇ s, it is difficult to achieve sufficient fluidity.
• the steric hindrance of the alkyl group derived from the compound of formula (a) and the orientation of the hydroxyl group derived from the compound of formula (b) (having a hydroxyl group at the ortho position of the aldehyde) are utilized to control the gel time during curing, thereby improving fluidity. If the gel time during curing is too short, the resin will not flow well during molding.
• the epoxy resin of this embodiment contains 75 to 95 area % of a compound represented by the following formula (d), as detected by a differential refractometer in gel permeation chromatography analysis. If the content of the compound represented by the following formula (d) is less than 75 area %, the epoxy resin of this embodiment and the curable resin composition containing it may not exhibit sufficient fluidity. If it exceeds 95 area %, the epoxy resin of this embodiment and the curable resin composition containing it may not exhibit sufficient heat resistance, and may exhibit high crystallinity and reduced solvent solubility.
• a compound represented by the following formula (d) is less than 75 area %, the epoxy resin of this embodiment and the curable resin composition containing it may not exhibit sufficient fluidity. If it exceeds 95 area %, the epoxy resin of this embodiment and the curable resin composition containing it may not exhibit sufficient heat resistance, and may exhibit high crystallinity and reduced solvent solubility.
• R groups each independently represent a hydrocarbon group having 1 to 5 carbon atoms.
• the total number of carbon atoms in the multiple R groups is 2 to 8.
• k is an integer from 1 to 3.
• the preferred values for R and k are the same as in the above formula (a).
• a representative structure of the epoxy resin of this embodiment can be represented by the following formula (d-1).
• multiple Rs each independently represent a hydrocarbon group having 1 to 5 carbon atoms.
• the total number of carbon atoms in the multiple Rs is 2 to 8.
• k is an integer from 1 to 3.
• n is the average number of repetitions and is 1 to 20.
• the preferred values for R, k, and n are the same as those in the above formula (c-1).
• the curable resin composition of this embodiment will be described below.
• the epoxy resin used in the curable resin composition of this embodiment may be the epoxy resin of this embodiment described above, which may be used alone, or may be used in combination with other epoxy resins.
• the proportion of the epoxy resin of this embodiment in the total epoxy resin is preferably 10 to 98 mass%, more preferably 30 to 95 mass%, and even more preferably 60 to 95 mass%.
• polycondensates of the phenols with aromatic dimethanols (benzenedimethanol, biphenyldimethanol, etc.); polycondensates of the phenols with aromatic dichloromethyls ( ⁇ , ⁇ '-dichloroxylene, bischloromethylbiphenyl, etc.); polycondensates of the phenols with aromatic bisalkoxymethyls (bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.); glycidyl ether epoxy resins, alicyclic epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins obtained by glycidylating polycondensates of the bisphenols with various aldehydes or alcohols, etc., but the epoxy resins are not limited to these, so long as they are commonly used.
• Curating agents that can be used in the curable resin composition of this embodiment include amine-based curing agents, acid anhydride-based curing agents, amide-based curing agents, phenol-based curing agents, and the active ester compounds described below.
• Specific examples of curing agents that can be used include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 2,2'-diaminodiphenylsulfone, diethyltoluenediamine, dimethylthiotoluenediamine, diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphen
• aliphatic amines such as 1,3-bis(aminomethyl)cyclohexane, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), norbornanediamine, ethylenediamine, propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, dimer diamine, metaxylylenediamine, and triethylenetetramine.
• aromatic amines are preferred, while aliphatic amines are preferred when rapid curing is desired.
• amide compounds such as polyamide resins synthesized from dicyandiamide, a dimer of linolenic acid, and ethylenediamine; acid anhydride compounds such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols (phenol, a polycondensates of alkyl substituted phenols, aromatic substituted phenols, naphthol, alkyl-substitute
• active ester compound refers to a compound containing at least one ester bond in its structure, with an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond.
• active ester compounds include compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. These compounds are obtained by a condensation reaction between at least one of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound and at least one of a hydroxy compound or a thiol compound.
• active ester compounds are particularly preferred when obtained from a carboxylic acid compound or an acid chloride and a hydroxy compound, with phenol compounds or naphthol compounds being preferred as the hydroxy compound.
• the active ester compounds may be used singly or in combination of two or more.
• carboxylic acid compound examples include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
• Examples of the acid chlorides include acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, and 4,4'-azodibenzoyl dichloride.
• phenol compounds and naphthol compounds examples include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, and the phenolic resins described below.
• dicyclopentadiene-type diphenol compounds refer to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.
• active ester compounds include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolac, active ester compounds containing a benzoylated phenol novolac, the compound described in Example 2 of WO 2020/095829, and the compounds disclosed in WO 2020/059625.
• active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred.
• the dicyclopentadiene-type diphenol structure refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.
• active ester compounds include, for example, "EXB9451,” “EXB9460,” “EXB9460S,” “HPC-8000-65T,” “HPC-8000H-65TM,” “EXB-8000L-65TM,” and “EXB-8150-65T” (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure; “EXB9416-70BK” (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure; and “EXB9416-70BK” (manufactured by DIC Corporation) as an active ester compound containing a phenol structure.
• active ester compounds containing acetylated phenol novolac include “DC808” (manufactured by Mitsubishi Chemical Corporation); active ester compounds containing benzoylated phenol novolac include “YLH1026,” “YLH1030,” and “YLH1048” (manufactured by Mitsubishi Chemical Corporation); an active ester curing agent containing phosphorus atoms is “EXB-9050L-62M” (manufactured by DIC Corporation); and an active ester compound containing a bisphenol A structure is "Unifiner W-575.”
• the amount of curing agent used is preferably 0.5 to 1.5 equivalents per equivalent of epoxy groups in the epoxy resin, and particularly preferably 0.6 to 1.2 equivalents. By using an amount of 0.5 to 1.5 equivalents, good curing properties can be obtained.
• curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole; tertiary amines such as 2-(dimethylaminomethyl)phenol, triethylenediamine, triethanolamine, and 1,8-diazabicyclo(5,4,0)undecene-7; organic phosphines such as triphenylphosphine, diphenylphosphine, and tributylphosphine; metal compounds such as tin octoate; tetra-substituted phosphonium tetra-substituted borates such as tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium ethyltri
• inorganic fillers can be added to the curable resin composition of this embodiment as needed.
• inorganic fillers include, but are not limited to, powders such as crystalline silica, fused silica, hollow silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, clay, zirconia, fosterite, steatite, spinel, titania, talc,
• these inorganic fillers may be used alone or in combination of two or more.
• the amount of these inorganic fillers used varies depending on the application, but for example, when used as a semiconductor encapsulant, it is preferable to use them in a proportion of 20% by mass or more of the curable resin composition, more preferably 30% by mass or more, in terms of the heat resistance, moisture resistance, mechanical properties, and flame retardancy of the cured product of the curable resin composition, and even more preferably 70 to 95% by mass, particularly to improve the linear expansion coefficient with the lead frame.
• the curable resin composition of this embodiment can be blended with a release agent to improve release from the mold during molding.
• a release agent to improve release from the mold during molding.
• Any of the conventionally known release agents can be used, including ester waxes such as carnauba wax and montan wax, fatty acids such as stearic acid and palmitic acid and their metal salts, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. These may be used alone or in combination of two or more.
• the amount of these release agents blended is preferably 0.5 to 3 mass% of the total organic components. If the amount is less than this, release from the mold will be poor, and if it is too much, adhesion to a lead frame, etc. will be poor.
• the curable resin composition of this embodiment can be formulated with a coupling agent to improve adhesion between the inorganic filler and the resin component.
• a coupling agent can be used, including various alkoxysilane compounds such as vinylalkoxysilane, epoxyalkoxysilane, styrylalkoxysilane, methacryloxyalkoxysilane, acryloxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, and isocyanatoalkoxysilane, as well as alkoxytitanium compounds and aluminum chelates. These may be used alone or in combination of two or more.
• the coupling agent can be added by first treating the surface of the inorganic filler with the coupling agent and then kneading it with the resin, or by mixing the coupling agent with the resin and then kneading the inorganic filler.
• known additives can be blended into the curable resin composition of this embodiment as needed.
• usable additives include polybutadiene and modified polybutadiene, modified acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compounds, cyanate ester compounds, silicone gel, silicone oil, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.
• the curable resin composition of this embodiment may also contain the following components.
• examples include carboxylic acid compounds, maleimide compounds, cyanate compounds, isocyanate compounds, polyphenylene ether compounds, compounds having ethylenically unsaturated bonds, polyamide compounds, polyimide compounds, allyl compounds, polybutadiene and modified products thereof, polystyrene and modified products thereof, polyethylene and modified products thereof, benzoxazine compounds, flame retardants, and polymerization initiators. These compounds may be used alone or in combination.
• polyphenylene ether compounds compounds having ethylenically unsaturated bonds, cyanate ester resins, polybutadiene and modified products thereof, polystyrene and modified products thereof, benzoxazine compounds, flame retardants, and polymerization initiators are preferred for achieving a balance of heat resistance, adhesion, and dielectric properties.
• the inclusion of these compounds can improve the brittleness of the cured product and adhesion to metals, thereby suppressing package cracking during solder reflow and reliability tests such as thermal cycling.
• the total amount of the above compounds used is preferably 10 times or less by mass, more preferably 5 times or less by mass, and particularly preferably 3 times or less by mass relative to the compound of this embodiment.
• the lower limit is preferably 0.1 times or more by mass, more preferably 0.25 times or more by mass, and even more preferably 0.5 times or more by mass.
• carboxylic acid compound examples include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicar
• maleimide compound examples include phenylmaleimide, 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, and Xylox-type maleimide compounds (anilix).
• maleimide manufactured by Mitsui Chemicals Fine Co., Ltd.
• biphenylaralkyl-type maleimide compounds solidified by distilling off the solvent under reduced pressure from a resin solution containing the maleimide compound (M2) described in Example 4 of JP 2009-001783 A), bisaminocumylbenzene-type maleimide (maleimide compounds described in WO 2020/054601 A), maleimide compounds having an indane structure described in JP 6629692 A or WO 2020/217679 A, polymaleimides derived from aromatic vinyl compounds and anilines described in JP 2023-007239 A, and the like, as described in MATERIAL STAGE Vol. 18, No.
• the cyanate compound is a cyanate compound obtained by reacting a phenol compound with a cyanogen halide, and specific examples include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and a phenol-dicyclopentadiene
• CYTESTER TA bisphenol A type cyanate resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.
• CYTESTER TA bisphenol A type cyanate resin, manufactured by Mitsubishi Gas Chemical Co., Ltd.
• these may be used alone or in combination.
• the cyanate compound whose synthesis method is described in Japanese Patent Application Laid-Open No. 2005-264154 is particularly preferred as the cyanate compound because it has low moisture absorption, flame retardancy, and excellent dielectric properties.
• the cyanate compound may contain a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, or dibutyltin maleate, if necessary, in order to trimerize the cyanate group to form a sym-triazine ring.
• a catalyst such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, or dibutyltin maleate, if necessary, in order to trimerize the cyanate group to form a sym-triazine ring.
• the catalyst is preferably used in an amount of 0.0001 to 0.10 parts by mass, and more preferably 0.00015 to 0.0015 parts by mass, per 100 parts by mass of the cyanate compound and curable resin composition.
• the isocyanate compound is a compound having two or more isocyanate groups in the molecule.
• the isocyanate compound include aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more biuret compounds
• the polyphenylene ether compound is preferably a polyphenylene ether compound having an ethylenically unsaturated bond, and more preferably a polyphenylene ether compound having an acrylic group, a methacrylic group, or a styrene structure.
• Commercially available products include SA-9000 (manufactured by SABIC Corporation, a polyphenylene ether compound having a methacrylic group), OPE-2St 1200, and OPE-2st 2200 (all manufactured by Mitsubishi Gas Chemical Company, Inc., polyphenylene ether compounds having a styrene structure).
• the number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5,000, more preferably 2,000 to 5,000, and even more preferably 2,000 to 4,000. If the number average molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. On the other hand, if the number average molecular weight is greater than 5,000, the melt viscosity increases, and sufficient fluidity cannot be obtained, which tends to result in molding defects. In addition, the reactivity decreases, the curing reaction takes a long time, and the amount of unreacted material that is not incorporated into the curing system increases, which tends to lower the glass transition temperature of the cured product and reduce the heat resistance of the cured product.
• the number average molecular weight of the polyphenylene ether compound is 500 to 5000, it is possible to exhibit excellent heat resistance, moldability, etc. while maintaining excellent dielectric properties.
• the number average molecular weight here can be specifically measured using gel permeation chromatography or the like.
• the polyphenylene ether compound may be obtained by a polymerization reaction or by a redistribution reaction of a high-molecular-weight polyphenylene ether compound with a number-average molecular weight of approximately 10,000 to 30,000. These compounds may also be used as raw materials and imparted with radical polymerization properties by reacting them with a compound having an ethylenically unsaturated bond, such as methacrylic acid chloride, acrylic acid chloride, or chloromethylstyrene.
• a polyphenylene ether compound obtained by a redistribution reaction may be obtained, for example, by heating a high-molecular-weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenolic compound and a radical initiator to cause a redistribution reaction.
• Polyphenylene ether compounds obtained by such a redistribution reaction are preferred because they maintain even higher heat resistance due to the presence of hydroxyl groups derived from phenolic compounds that contribute to curing at both ends of the molecular chain.
• functional groups can be introduced at both ends of the molecular chain even after modification with a compound having an ethylenically unsaturated bond.
• polyphenylene ether compounds obtained by a polymerization reaction are preferred because they exhibit excellent fluidity.
• the molecular weight of the resulting polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc.
• the molecular weight of the resulting polyphenylene ether compound can be adjusted by adjusting the conditions, etc. of the redistribution reaction. More specifically, one possible approach is to adjust the amount of phenolic compound used in the redistribution reaction. That is, the greater the amount of phenolic compound used, the lower the molecular weight of the resulting polyphenylene ether compound.
• poly(2,6-dimethyl-1,4-phenylene ether) or the like can be used as a high-molecular-weight polyphenylene ether compound that undergoes the redistribution reaction.
• the phenolic compound used in the redistribution reaction is not particularly limited, but preferred are, for example, multifunctional phenolic compounds having two or more phenolic hydroxyl groups per molecule, such as bisphenol A, phenol novolac, and cresol novolac. These compounds may be used alone or in combination.
• the content of the polyphenylene ether compound is not particularly limited, but is preferably 5 to 1,000 parts by mass, and more preferably 10 to 750 parts by mass, per 100 parts by mass of the curable resin composition.
• a polyphenylene ether compound content within the above range is preferable in that it not only has excellent heat resistance, but also allows for a cured product that fully exhibits the excellent dielectric properties of the polyphenylene ether compound.
• the compound containing an ethylenically unsaturated bond is a compound having one or more ethylenically unsaturated bonds in the molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used or not.
• Examples of the compound containing an ethylenically unsaturated bond include acenaphthylene, indene, styrene, divinylbenzene, reaction products of the phenol resins with ethylenically unsaturated bond-containing halogen-based compounds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.), reaction products of ethylenically unsaturated bond-containing phenols (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) with halogen-based compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophen
• polyamide resin examples include reaction products of one or more of diamines, diisocyanates, and oxazolines with dicarboxylic acids, reaction products of diamines with acid chlorides, and ring-opening polymerization products of lactam compounds. These may be used alone or in combination. Specific examples of the above raw materials are given below, but are not limited to these.
• ⁇ Diisocyanate> benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl)methane, isophorone diisocyanate, 1,3-bis(2-isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, and the like.
• ⁇ Dicarboxylic acid> Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, and the like.
• ⁇ Acid chloride Acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azodibenzoyl dichloride and the like.
• ⁇ Lactam > ⁇ -caprolactam, ⁇ -undecanelactam, ⁇ -laurolactam, and the like.
• polyimide resin examples include, but are not limited to, reaction products of the diamines described above with the tetracarboxylic dianhydrides listed below. These may be used alone or in combination. Specific examples include polyimide compounds obtained by the method described in WO2023013224A1.
• allyl compounds examples include monoallyl isocyanurate, diallyl isocyanurate, triallyl isocyanurate, etc. Specific examples include “TAIC” (manufactured by Mitsubishi Chemical Corporation), “MA-DGIC”, and “DA-MGIC” (all manufactured by Shikoku Chemicals Corporation).
• Polybutadiene and its modified products are polybutadiene or compounds having a structure derived from polybutadiene in the molecule.
• the unsaturated bonds in the polybutadiene-derived structure may be partially or entirely converted to single bonds by hydrogenation.
• Examples of polybutadiene and modified polybutadienes include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, (meth)acrylate-terminated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, and styrene-butadiene rubber. These may be used alone or in combination.
• polybutadiene or styrene-butadiene rubber is preferred from the viewpoint of dielectric properties.
• styrene-butadiene rubber examples include RICON-100, RICON-181, and RICON-184 (all manufactured by Cray Valley Chemical Industries, Ltd.) and 1,2-SBS (manufactured by Nippon Soda Co., Ltd.).
• polybutadienes examples include B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda Co., Ltd.).
• the molecular weight of polybutadiene and styrene-butadiene rubber is preferably a weight-average molecular weight of 500 to 10,000, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000.
• the amount of volatilization is high, making it difficult to adjust the solids content during prepreg production.
• compatibility with other curable resins deteriorates.
• compounds containing heteroatoms such as oxygen and nitrogen such as bismaleimides and polymaleimides, have difficulty ensuring compatibility with low-polarity compounds, such as compounds composed primarily of hydrocarbons or compounds composed solely of hydrocarbons, due to their polarity.
• the compound of this embodiment does not have a skeleton design that actively incorporates heteroatoms such as oxygen and nitrogen, and therefore exhibits excellent compatibility with materials with low polarity and low dielectric properties, as well as compounds composed solely of hydrocarbons.
• Polystyrene and its modified products are polystyrene or compounds having a structure derived from polystyrene in the molecule.
• examples of polystyrene and modified products thereof include polystyrene, styrene-2-isopropenyl-2-oxazoline copolymers (Epocross RPS-1005, RP-61, both manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon (registered trademark) 1020, manufactured by Kuraray Co., Ltd.), SEPS (styrene-ethylene-propylene-styrene copolymer: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, all manufactured by Kuraray Co., Ltd.), and SEEPS (styrene-ethylene/ethylene-propylene-styrene block copo
• SEBS styrene-ethylene-butylene-styrene block copolymer: Septon 8004, Septon 8006, Septon 8007L, all manufactured by Kuraray Co., Ltd.
• SEEPS-OH styrene-ethylene/ethylene-propylene-styrene block copolymer with a hydroxyl group at the end: Septon HG252, manufactured by Kuraray Co., Ltd.
• SIS styrene-isoprene-styrene block copolymer: Septon 5125, Septon 5127, all manufactured by Kuraray Co., Ltd.
• hydrogenated SIS hydrogenated styrene-isoprene-styrene block copolymer: Hybrar (registered trademark) 7125F, Hybrar 7311F
• suitable polystyrenes include, but are not limited to, SIBS (styrene-isobutylene-styrene block copolymer: Sept
• Polystyrene and modified products thereof have higher heat resistance and are less susceptible to oxidative degradation, and therefore preferably do not have unsaturated bonds.
• weight-average molecular weight of polystyrene and modified products thereof There are no particular restrictions on the weight-average molecular weight of polystyrene and modified products thereof, as long as they are 10,000 or more. However, if the weight-average molecular weight is too large, compatibility with polyphenylene ether compounds, low-molecular-weight components with a weight-average molecular weight of about 50 to 1,000, and oligomer components with a weight-average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, a weight-average molecular weight of about 10,000 to 300,000 is preferred.
• Polyethylene and its modified products are compounds having polyethylene or a structure derived from polyethylene in the molecule.
• Examples of polyethylene and modified polyethylenes include ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylidene norbornene copolymers (EBT: K-8370EM, K-9330M, etc., manufactured by Mitsui Chemicals, Inc.), ethylene-propylene-vinyl norbornene copolymers (VNB-EPT: PX-006M, PX-008M, PX-009M, etc., manufactured by Mitsui Chemicals, Inc.), ethylene-vinyl alcohol copolymers, and ethylene-vinyl acetate copolymers, but are not limited thereto.
• ethylene-propylene-ethylidene norbornene copolymers or ethylene-propylene-vinyl norbornene copolymers containing a crosslinkable structure may be used alone or in combination.
• weight-average molecular weight of polyethylene and modified polyethylenes thereof there are no particular restrictions on the weight-average molecular weight of polyethylene and modified polyethylenes thereof as long as it is 10,000 or more.
• compatibility with not only the polyphenylene ether compound but also low-molecular-weight components having a weight-average molecular weight of about 50 to 1,000 and oligomer components having a weight-average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, it is preferably about 10,000 to 300,000.
• any compound may be used as long as it is a compound obtained by reacting a compound having a phenolic hydroxyl group, a compound having an amino group, or a compound having an aldehyde group.
• the compound having a phenolic hydroxyl group is not particularly limited, but for example, the above-mentioned phenolic resin, phenols (which may have a substituent such as an alkenyl group or an alkyl group), and bisphenols can be used.
• the compound having an amino group is not particularly limited, but the above-mentioned amine resin, diamine, and anilines (which may have a substituent such as an alkenyl group or an alkyl group) can be used.
• the aldehyde compound for example, the above-mentioned aldehydes can be used, but formaldehyde is preferably used.
• benzoxazine compounds may be used, and examples thereof include benzoxazine P-d, Fa, and ALP-d (all manufactured by Shikoku Chemical Industry Co., Ltd.), JBZ-BA100N, JBZ-FA100N, JBZ-DP100N, JBZ-OP100N, JBZ-OP100D, and JBZ-OP100I (all manufactured by JFE Chemical Corporation), and BTBz (manufactured by Japan Material Technology Co., Ltd.).
• the curable resin composition of the present embodiment may contain a flame retardant.
• the flame retardant include halogen-based flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), and phosphorus-based flame retardants. From the viewpoint of achieving halogen-free flame retardancy, phosphorus-based flame retardants are preferred.
• the phosphorus-based flame retardants may be either reactive or additive.
• Specific examples include, but are not limited to, phosphate esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis(dixylylenyl phosphate), 1,4-phenylenebis(dixylylenyl phosphate), and 4,4'-biphenyl(dixylylenyl phosphate); phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; phosphorus-containing epoxy compounds obtained by reacting epoxy resin with the active hydrogen of the
• phosphate esters, phosphanes, or phosphorus-containing epoxy compounds are preferred, with 1,3-phenylenebis(dixylilenyl phosphate), 1,4-phenylenebis(dixylilenyl phosphate), 4,4'-biphenyl(dixylilenyl phosphate), or phosphorus-containing epoxy compounds being particularly preferred.
• the content of flame retardant is preferably in the range of 0.1 to 0.6 parts by mass per 100 parts by mass of the curable resin composition. If it is less than 0.1 part by mass, the flame retardancy may be insufficient, and if it is more than 0.6 part by mass, it may have a negative effect on the moisture absorption and dielectric properties of the cured product.
• the curability of the curable resin composition of this embodiment can be improved by adding a polymerization initiator.
• the polymerization initiator is a compound capable of polymerizing an olefin functional group such as an ethylenically unsaturated bond, and examples thereof include an olefin metathesis polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, and a radical polymerization initiator. Among these, it is preferable to use a radical polymerization initiator that has curability and appropriate stability.
• the radical polymerization initiator is a compound that generates radicals upon irradiation with ultraviolet or visible light or heating, thereby initiating a chain polymerization reaction.
• Usable radical polymerization initiators include organic peroxides, azo compounds, and benzopinacols.
• Organic peroxides are preferred because they are effective in controlling the curing temperature, suppress outgassing, and minimize the impact of decomposition products on electrical properties.
• organic peroxides include, for example, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dialkyl peroxides such as dicumyl peroxide (DCP) and 1,3-bis-(t-butylperoxyisopropyl)-benzene, peroxyketals such as t-butyl peroxybenzoate and 1,1-di-t-butylperoxycyclohexane, ⁇ -cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and t-amylperoxy-2-ethylhexanoate.
• ketone peroxides such as methyl ethyl ket
• peroxycarbonate examples include alkyl peresters such as di-2-ethylhexyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, and t-amylperoxybenzoate, peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxyisopropyl carbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, and lauroyl peroxide.
• alkyl peresters such as di-2-ethylhexy
• Irgacure OXE-04 and Irgacure 290 both manufactured by BASF. These may be used alone or in combination.
• organic peroxides ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, peroxycarbonates, etc. are preferred, with dialkyl peroxides being more preferred.
• azo compounds examples include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile). These compounds may be used alone or in combination.
• the amount of polymerization initiator added is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass, per 100 parts by mass of the curable resin composition. If the amount of polymerization initiator used is less than 0.01 part by mass, there is a risk that the molecular weight will not be sufficiently extended during the polymerization reaction, and if it is more than 5 parts by mass, there is a risk that the dielectric properties such as the dielectric constant and dielectric loss tangent will be impaired.
• the curable resin composition of this embodiment may contain a polymerization inhibitor.
• a polymerization inhibitor improves storage stability and enables control of the reaction initiation temperature. Controlling the reaction initiation temperature makes it easier to ensure fluidity, prevents impregnation into glass cloth or the like from being impaired, and facilitates B-staging, such as prepreg formation. If the polymerization reaction proceeds too much during prepreg formation, problems such as difficulty in lamination during the lamination process are likely to occur.
• the polymerization inhibitor may be added during or after the synthesis of the compound of this embodiment.
• the amount of polymerization inhibitor used is 0.008 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, per 100 parts by weight of the compound of this embodiment.
• polymerization inhibitors examples include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based inhibitors.
• One type of polymerization inhibitor may be used, or multiple types may be used in combination. Of these, in this embodiment, phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based inhibitors are preferred.
• phenolic polymerization inhibitors include, for example, monophenols such as 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl- ⁇ -(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and 2,4-bis[(octylthio)methyl]-o-cresol; t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol),
• sulfur-based polymerization inhibitor examples include, but are not limited to, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate.
• Examples of the phosphorus-based polymerization inhibitors include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis(octadecyl) phosphite, cyclic neopentanetetraylbis(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis(2,4-di-t-butyl-4-methylphenyl) phosphite, bis[2- Examples of suitable phosphites include t-buty
• Examples of the above hindered amine polymerization inhibitors include ADK STAB (registered trademark) LA-40MP, ADK STAB LA-40Si, ADK STAB LA-402AF, ADK STAB LA-87, ADK STAB LA-82, ADK STAB LA-81, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-72, ADK STAB LA-68, ADK STAB LA-63P, ADK STAB LA-57, and ADK STAB LA-52 (all manufactured by ADE Corporation).
• ADK STAB registered trademark
• LA-40MP registered trademark
• ADK STAB LA-40Si AdK STAB LA-402AF
• ADK STAB LA-87 ADK STAB LA-82
• ADK STAB LA-81 ADK STAB LA-77Y
• ADK STAB LA-77G ADK STAB LA-72
• ADK STAB LA-68 ADK STAB LA-63P
• ADK STAB LA-57 and ADK STAB LA-
• suitable solvents include, but are not limited to, Chimassorb (registered trademark) 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin (registered trademark) 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, and Tinuvin 791FB (all manufactured by BASF).
• nitroso-based polymerization inhibitor examples include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, and the ammonium salt (cupferron) of N-nitrosophenylhydroxyamine. Of these, the ammonium salt (cupferron) of N-nitrosophenylhydroxyamine is preferred.
• nitroxyl radical polymerization inhibitor examples include, but are not limited to, di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl.
• the curable resin composition of the present embodiment may contain a light stabilizer.
• a light stabilizer a hindered amine light stabilizer (Hindered Amine Light Stabilizers, HALS) or the like is preferable.
• HALS include a reaction product of dibutylamine, 1,3,5-triazine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, a polycondensation product of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, and poly[ ⁇ 6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl ⁇ (2,2,6,6-tetramethyl-4-piperidyl)imino ⁇ hexamethylene ⁇ (2,2,2,
• Suitable hydroxybenzyl compounds include, but are not limited to, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, and bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate. These compounds may be used alone or in combination.
• the content of the light stabilizer is preferably in the range of 0.001 to 0.1 parts by mass per 100 parts by mass of the curable resin composition. Less than 0.001 parts by mass may be insufficient to achieve light stabilization, while more than 0.1 parts by mass may have a negative impact on the moisture absorption and dielectric properties of the cured product.
• the curable resin composition of this embodiment is obtained by uniformly mixing the above components.
• the curable resin composition of this embodiment can be easily cured using methods similar to those known in the art.
• the curable resin composition of this embodiment can be obtained by thoroughly mixing the epoxy resin and curing agent, and optionally a curing accelerator, inorganic filler, mold release agent, silane coupling agent, and additives, using an extruder, kneader, roll, or the like as needed until uniform, and then molding this composition using a melt casting method, transfer molding method, injection molding method, compression molding, or the like, and further heating at 80 to 200°C for 2 to 10 hours to obtain a cured product.
• the curable resin composition of this embodiment may also contain a solvent, if necessary.
• the solvent-containing curable resin composition epoxy resin varnish
• a fibrous material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and the resulting prepreg can be heat-dried and hot-press molded to produce a cured product of the curable resin composition of this embodiment.
• the solvent content of this curable resin composition is typically 10 to 70% by mass, and preferably about 15 to 70% by mass.
• solvents include gamma-butyrolactones; amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylimidazolidinone; sulfones such as tetramethylene sulfone; ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monobutyl ether, preferably mono- or di-lower (1 to 3 carbon atoms) alkyl ethers of lower (1 to 3 carbon atoms) alkylene glycols; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, preferably di-lower (1 to 3 carbon atoms) alkyl ketones in which the two alkyl groups may be the same or different; and aromatic
• a sheet-like adhesive can be obtained by applying the epoxy resin varnish to a release film, removing the solvent under heat, and then B-staging the material.
• This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates, etc.
• thermosetting resins such as epoxy resins are used, such as adhesives, paints, coatings, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, electrical wire coatings, etc.), sealants, and additives for other resins, etc.
• Adhesives include those for civil engineering, construction, automotive, general office, and medical use, as well as adhesives for electronic materials.
• adhesives for electronic materials include interlayer adhesives for multilayer boards such as build-up boards, die bonding agents, semiconductor adhesives such as underfill, underfill for reinforcing BGA, and mounting adhesives such as anisotropic conductive film (ACF) and anisotropic conductive paste (ACP).
• ACF anisotropic conductive film
• ACP anisotropic conductive paste
• Sealants include potting, dipping, and transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, and LSIs; potting sealing for COB, COF, and TAB of ICs and LSIs; underfill for flip chips; and sealing (including reinforcing underfill) when mounting IC packages such as QFP, BGA, and CSP.
• Example 2 A flask equipped with a thermometer, a condenser, and a stirrer was purged with nitrogen, and 1,305 parts of epichlorohydrin, 386 parts of dimethyl sulfoxide, and 23 parts of water were added to 407 parts of the phenolic resin (P1) obtained in Example 1, and the internal temperature was raised to 45°C. 114 parts of sodium hydroxide were added in portions over 3 hours, and the reaction was carried out at 45°C for 1.5 hours and at 70°C for 0.5 hours. The solvent and excess epichlorohydrin were distilled off under reduced pressure, and 1,280 parts of methyl isobutyl ketone was added.
• a GPC chart of the obtained epoxy resin (E1) is shown in Figure 2 (the number average molecular weight Mn was 593, and the weight average molecular weight Mw was 644).
• the total value of the peak areas derived from the raw materials, the reaction product of 3-methyl-6-t-butylphenol and epihalohydrin, and the reaction product of 4-methyl-2-t-butylphenol and epihalohydrin, was 0.3 area%, the peak area derived from the component of the compound represented by formula (d-2) below, where n 1, was 86.0 area%, and the peak area derived from compounds higher in molecular weight than the compound represented by formula (d-2) below was 13.7 area%.
• Example 3 and Comparative Example 1 The epoxy resin (E1) obtained in Example 2 and an epoxy resin represented by the following formula (e) (FAE-2500, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 216 g/eq., softening point 86°C, ICI viscosity at 150°C 0.29 Pa s), a phenol novolak resin (PN(H-1), manufactured by Meiwa Kasei Co., Ltd., softening point 85°C, hydroxyl equivalent 104 g/eq.) as a curing agent, and triphenylphosphine (hereinafter also referred to as TPP) as a curing accelerator were used, and these were compounded in the proportions (parts by weight) shown in Table 1, and the mixture was uniformly mixed and kneaded using a mixing roll. After demolding, the mixture was cured at 160°C for 2 hours and then at 180°C for 6 hours to obtain a test piece for evaluation.
• e phenol novolak
• Example 3 which is a curable resin composition of the present invention, was confirmed to have excellent fluidity in terms of its long gel time and the long period for which low viscosity can be maintained after melting. Furthermore, the cured product had a glass transition temperature of 200°C or higher, indicating good heat resistance, and it was also confirmed to have excellent elastic modulus and low water absorption.
• the epoxy resin of the present invention is suitable for use in electric and electronic parts such as semiconductor encapsulants, printed wiring boards, build-up laminates, and optical waveguide devices.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Epoxy Resins (AREA)
• Epoxy Compounds (AREA)

Priority Applications (1)

Applications Claiming Priority (4)

Publications (1)

Family

ID=97139472

Family Applications (1)

Country Status (3)

Citations (6)

• 2025
  • 2025-02-27 WO PCT/JP2025/006773 patent/WO2025197458A1/ja active Pending
  • 2025-02-27 JP JP2025545829A patent/JP7842313B2/ja active Active
  • 2025-02-27 TW TW114107266A patent/TW202537992A/zh unknown

Patent Citations (6)

Also Published As

Similar Documents

Legal Events