WO2016052290A1 - エポキシ樹脂組成物及びその硬化物 - Google Patents
エポキシ樹脂組成物及びその硬化物 Download PDFInfo
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- WO2016052290A1 WO2016052290A1 PCT/JP2015/076889 JP2015076889W WO2016052290A1 WO 2016052290 A1 WO2016052290 A1 WO 2016052290A1 JP 2015076889 W JP2015076889 W JP 2015076889W WO 2016052290 A1 WO2016052290 A1 WO 2016052290A1
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- epoxy resin
- resin composition
- resin
- phenol
- phenol resin
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- 0 *c(cc1Cc2cc(*)ccc2O)ccc1O Chemical compound *c(cc1Cc2cc(*)ccc2O)ccc1O 0.000 description 1
- VZJOGDYZRPMGSG-UHFFFAOYSA-N CCNc1nc(NC)nc(N)n1 Chemical compound CCNc1nc(NC)nc(N)n1 VZJOGDYZRPMGSG-UHFFFAOYSA-N 0.000 description 1
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- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
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- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- 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
- C08G59/40—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 curing agents used
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- 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
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- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- H05K1/0313—Organic insulating material
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- H05K1/0313—Organic insulating material
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
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Definitions
- the present invention relates to an epoxy resin composition that exhibits excellent flame retardancy and heat resistance in a cured product, as well as excellent dielectric properties such as low dielectric loss tangent and low dielectric constant, and further excellent thermal conductivity.
- thermosetting resin such as an epoxy resin type, a benzoxazine resin type, a BT (bismaleimide-triazine) resin type, and prepreg obtained by heating and drying, the prepreg
- a laminated board obtained by heat-curing, a multilayer board obtained by combining the laminated board and the prepreg and heat-cured is widely used.
- thermosetting system that is halogen-free and exhibits excellent flame retardancy
- a triazine ring-containing phenol resin obtained by reacting an epoxy resin curing agent with an amino group-containing triazine compound, phenols, and aldehydes is used.
- a technique to be used has been proposed (for example, see Patent Document 1 below).
- these triazine ring-containing phenol resins exhibit good flame retardancy when used in combination with phosphorus flame retardants, etc., but have sufficient flame retardancy without the combined use of added flame retardants and flame retardant aids. It did not lead to expression.
- the trend toward higher frequencies in electronic components in recent years is remarkable, and resin materials having a lower dielectric constant and dielectric loss tangent are required for insulating materials such as semiconductor encapsulants, copper-clad laminates, and build-up films.
- the triazine ring-containing phenol resin does not sufficiently satisfy the required level.
- An object of the present invention is an epoxy resin composition that exhibits excellent flame retardancy and heat resistance in a cured product, as well as excellent dielectric properties such as low dielectric loss tangent and low dielectric constant, and further excellent thermal conductivity, And providing a cured product thereof.
- the present inventors use a triazine ring-containing phenol resin obtained by reacting para-alkylphenol, melamine and formalin as a curing agent for epoxy resin.
- the cured product exhibits excellent flame retardancy and heat resistance, and has excellent dielectric properties such as low dielectric loss tangent and low dielectric constant, and further provides excellent thermal conductivity, and completes the present invention. It came to.
- the present invention also relates to an epoxy resin composition containing an epoxy resin and the triazine ring-containing phenol resin as essential components.
- the present invention also includes a cured product obtained by curing the epoxy resin composition, impregnating a reinforcing substrate with a solution obtained by diluting the epoxy resin composition in an organic solvent, and semi-curing the resulting impregnated substrate.
- the obtained prepreg, a circuit board obtained by laminating the prepreg shaped into a plate shape with a copper foil, and heat-press molding, and the base material film obtained by diluting the epoxy resin composition in an organic solvent The build-up film obtained by applying and drying, and applying the build-up film to a circuit board on which a circuit is formed, and forming the unevenness on the circuit board obtained by heating and curing, and then plating the circuit board Build-up substrate obtained by performing, semiconductor sealing material containing the epoxy resin composition and inorganic filler, heat curing the semiconductor sealing material.
- an epoxy resin composition that provides excellent dielectric properties such as low dielectric loss tangent and low dielectric constant, and further excellent thermal conductivity, and its A cured product can be provided.
- the epoxy resin composition of the present invention when used in the field of electronic materials such as a resin composition for printed circuit boards, a resin composition for encapsulants for electronic parts, resist inks, conductive pastes, etc. In addition, it is extremely useful as a resin composition for high frequency and high speed computing.
- the obtained molded cured product has excellent flame retardancy, heat resistance, thermal conductivity, low dielectric loss tangent and low dielectric constant, and satisfies the high demands of the above-mentioned uses and further adhesives, composite materials, etc. It can be applied to fields that require high reliability.
- the triazine ring-containing phenol resin of the present invention has good solvent solubility.
- epoxy resin (A) used in the curable resin composition of the present invention will be described.
- examples of the epoxy resin (A) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol sulfide type epoxy resin, biphenyl type epoxy resin, and tetramethylbiphenyl type epoxy.
- Resin polyhydroxynaphthalene type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type Epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl novolac type epoxy resin, naphtholno Rack type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, biphenyl-modified phenol type epoxy resin (phenol skeleton and biphenyl skeleton are linked by bismethylene group) Other-valent phenolic epoxy resin), biphenyl-modified naphthol-type epoxy resin (other-valent naphthol-type epoxy resin in which naphthol ske
- a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a bisphenol A novolak type epoxy resin, a polyhydroxynaphthalene type epoxy resin, a triphenylmethane type epoxy resin in that a cured product having excellent heat resistance can be obtained.
- Tetraphenylethane type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin Resins, xanthene type epoxy resins and the like are preferable.
- a dicyclopentadiene-phenol addition reaction type epoxy resin a naphthol novolak type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl aralkyl type epoxy resin, a naphthol aralkyl type epoxy resin, in that a cured product having excellent dielectric properties can be obtained.
- biphenyl-modified phenol type epoxy resin
- phenol resin (B) is a triazine ring-containing phenol resin obtained by reacting para-alkylphenol, melamine and formalin. Specifically, a condensate of para-alkylphenol, melamine and formalin, a condensate of melamine and formalin, a condensate of para-alkylphenol and formalin, a mixture of para-alkylphenol and melamine.
- the content of the bifunctional compound represented by the formula is preferably in the range of 1 to 12% from the viewpoint of excellent flame retardancy.
- the molecular weight distribution (Mw / Mn) calculated from GPC measurement is preferably in the range of 1.35 to 1.85 from the viewpoint of excellent dielectric constant and dielectric loss tangent.
- the content of the bifunctional compound is calculated from the area ratio of the GPC chart measured under the following conditions. Further, the molecular weight distribution (Mw / Mn) is a value measured under the following GPC measurement conditions. ⁇ GPC measurement> The measurement was performed under the following conditions.
- Measuring device “HLC-8320 GPC” manufactured by Tosoh Corporation Column: Guard column “HXL-L” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + Tosoh Corporation “TSK-GEL G3000HXL” + “TSK-GEL G4000HXL” manufactured by Tosoh Corporation Detector: RI (differential refraction) detector
- Data processing “EcoSEC-WS version 1.12” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Developing solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used according to the measurement manual of “EcoSEC-WS version 1.12”.
- this invention is also an epoxy resin composition which contains an epoxy resin (A) and the said (Y) as an essential component.
- R in the structural formulas (II) and (III) is an alkyl group having 1 to 6 carbon atoms, and includes a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a secondary butyl group, and tertiary butyl.
- a tertiary butyl group is preferable because of its excellent performance such as heat resistance, dielectric properties, and flame retardancy. That is, it is preferable to use para-tertiary butylphenol as the para-alkylphenol.
- the triazine ring-containing phenol resin is obtained by reacting each component of para-alkylphenol, melamine and formalin.
- para-alkylphenol, melamine and formalin are used without any catalyst or in the presence of a catalyst.
- the method of making it react is mentioned.
- the order of reaction of each raw material is not particularly limited, and para-alkylphenol and formalin may be reacted first, and then melamine may be added. Conversely, formalin and melamine are reacted and then para-alkylphenol is added and reacted. May be. Alternatively, all the raw materials may be added and reacted at the same time.
- the molar ratio of melamine to para-alkylphenol is such that the reaction system is uniform and the reaction product is uniform, and the cross-linking density of the resulting cured product is appropriate, and the physical properties of the cured product are excellent.
- basic catalysts include, for example, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, barium hydroxide and the like, oxides thereof, ammonia, Tertiary amines, hexamethylenetetramine, sodium carbonate and the like can be mentioned.
- the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, sulfonic acid and phosphoric acid, organic acids such as oxalic acid and acetic acid, Lewis acids, and zinc acetate. And divalent metal salts.
- the epoxy resin composition of the present invention when used as a resin for electrical and electronic materials, it is preferable not to leave an inorganic substance such as a metal as a catalyst residue, so that the basic catalyst is triethylamine. It is preferable to use organic acids as amines and acidic catalysts.
- the above reaction may be performed in the presence of various solvents from the viewpoint of reaction control. If necessary, impurities such as salts may be removed by neutralization and washing with water, but impurities may not be removed when no catalyst is used or amines are used in the catalyst.
- condensed water, unreacted formalin, para-alkylphenol, solvent and the like are removed according to a conventional method such as atmospheric distillation or vacuum distillation.
- a conventional method such as atmospheric distillation or vacuum distillation.
- the triazine ring-containing phenol resin thus obtained is not limited in any way to the content of the remaining unreacted para-alkylphenol in the resin, but is preferably 5% by mass or less, and is cured. It is more preferably 3% by mass or less because the heat resistance and moisture resistance of the product are good.
- the triazine ring-containing phenol resin is particularly preferably in the range of a softening point of 75 to 200 ° C., and in the range of 75 to 180 ° C. from the viewpoint of excellent balance between flame retardancy and heat resistance. More preferred.
- the softening point is a value measured by a ring-and-ball method (according to “JIS K7234-86”, heating rate is 5 ° C./min).
- the mixing ratio of the epoxy resin (A) and the phenol resin (B) is the molar ratio of the epoxy group in the epoxy resin (A) to the phenolic hydroxyl group in the phenol resin (B) (epoxy group / phenol).
- the ratio is preferably 5 to 0.5 in terms of curability and heat resistance of the cured product.
- the epoxy resin composition of the present invention contains other heat A curable resin may be used in combination.
- the other thermosetting resins described above include cyanate ester resins, benzoxazine resins, maleimide compounds, active ester resins, vinyl benzyl compounds, acrylic compounds, and copolymers of styrene and maleic anhydride.
- the amount used is not particularly limited as long as the effect of the present invention is not impaired, but it is in the range of 1 to 50 parts by weight per 100 parts by weight of the thermosetting resin composition.
- the cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol P type cyanate ester resin, Bisphenol Z type cyanate ester resin, bisphenol AP type cyanate ester resin, bisphenol sulfide type cyanate ester resin, phenylene ether type cyanate ester resin, naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, Polyhydroxynaphthalene-type cyanate ester resin, phenol no
- cyanate ester resins bisphenol A-type cyanate ester resins, bisphenol F-type cyanate ester resins, bisphenol E-type cyanate ester resins, and polyhydroxynaphthalene-type cyanate ester resins are particularly preferred in that a cured product having excellent heat resistance can be obtained.
- a naphthylene ether type cyanate ester resin or a novolak type cyanate ester resin is preferably used, and a dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferred in that a cured product having excellent dielectric properties can be obtained.
- the benzoxazine resin is not particularly limited.
- a reaction product of bisphenol F, formalin and aniline Fa type benzoxazine resin
- a reaction product of diaminodiphenylmethane, formalin and phenol Pd type
- Benzoxazine resin reaction product of bisphenol A, formalin and aniline
- reaction product of dihydroxydiphenyl ether, formalin and aniline reaction product of diaminodiphenyl ether, formalin and phenol
- the maleimide compound include various compounds represented by any of the following structural formulas (i) to (iii).
- R is an m-valent organic group
- x and y are each a hydrogen atom, a halogen atom, an alkyl group, or an aryl group
- n is an integer of 1 or more.
- R is a hydrogen atom, alkyl group, aryl group, aralkyl group, halogen atom, hydroxyl group or alkoxy group, n is an integer of 1 to 3, and m is an average of 0 to 10 repeating units.
- R is a hydrogen atom, alkyl group, aryl group, aralkyl group, halogen atom, hydroxyl group or alkoxy group, n is an integer of 1 to 3, and m is an average of 0 to 10 repeating units.
- the active ester resin is not particularly limited, but generally an ester group having high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, is contained in one molecule. A compound having two or more is preferably used.
- the active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
- an active ester resin obtained from a carboxylic acid compound or a halide thereof and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or a halide thereof and a phenol compound and / or a naphthol compound is preferred. More preferred.
- the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like, or a halide thereof.
- phenol compounds or naphthol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, 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, phloroglucin Benzenetriol, dicyclopentadiene-phenol addition resin, and the like.
- the active ester resin examples include an active ester resin containing a dicyclopentadiene-phenol addition structure, an active ester resin containing a naphthalene structure, an active ester resin that is an acetylated product of phenol novolac, and an activity that is a benzoylated product of phenol novolac.
- An ester resin or the like is preferable, and an active ester resin having a dicyclopentadiene-phenol addition structure and an active ester resin having a naphthalene structure are more preferable because they are excellent in improving peel strength. More specifically, as an active ester resin containing a dicyclopentadiene-phenol addition structure, the following general formula (iv):
- R represents a phenyl group or a naphthyl group, k represents 0 or 1, and n represents an average of 0.05 to 2.5 repeating units.
- the compound represented by this is mentioned. From the viewpoint of reducing the dielectric loss tangent of the cured product of the resin composition and improving the heat resistance, R is preferably a naphthyl group, k is preferably 0, and n is preferably 0.25 to 1.5.
- the epoxy resin composition of the present invention includes an amine compound, an amide compound, an acid anhydride compound, phenol, as a curing agent for epoxy resin, in addition to the phenol resin (B), as long as the effects of the present invention are not impaired.
- the curing agent (Z) can be used by replacing a part of the phenol resin (B) with the curing agent (Z). That is, when the curing agent (Z) is used in combination, the total of active hydrogen in the curing agent (Z) and active hydrogen in the phenol resin (B) is 1 mol of epoxy groups in the epoxy resin (A). On the other hand, the ratio is preferably 0.2 to 2. Moreover, a hardening
- Examples of amine compounds that can be used here include metaxylenediamine, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivatives.
- Examples of the amide compounds include polyamide resins synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine.
- Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydroanhydride
- Examples include phthalic acid.
- the phenolic compound used as the curing agent (Z) includes phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, ⁇ -naphthol aralkyl. Resin, ⁇ -naphthol aralkyl resin, biphenyl aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, aminotriazine modified phenol resin, etc.
- the aminotriazine-modified phenolic resin is other than the phenolic resin (B) of the present invention. Specifically, a copolymer of an amino group-containing triazine compound such as melamine or benzoguanamine, phenol and formaldehyde. Is mentioned.
- polyhydric phenol compounds are particularly preferred because the linear expansion coefficient of the cured product is lower, and they are resistant to thermal and physical impacts and are excellent in toughness.
- Phenol novolac resins, cresol novolac resins, phenol aralkyl resins ⁇ -naphthol aralkyl resins, ⁇ -naphthol aralkyl resins, biphenyl aralkyl resins, and aminotriazine-modified phenol resins are preferred.
- the epoxy resin composition of the present invention has a curing accelerator (hereinafter referred to as “curing accelerator (C)” in order to rapidly advance the curing reaction between the epoxy resin (A) and the phenol resin (B).
- curing accelerator (C) examples include imidazoles, tertiary amines, and tertiary phosphines.
- imidazoles include 2-ethyl-4-methylimidazole, 2 -Methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2- Undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2- Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 Hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl- 2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenyl In addition to imidazole and the like,
- tertiary amines include trimethylamine, triethylamine, tripropylamine, tributylamine, tetramethylbutanediamine, tetramethylpentanediamine, tetramethylhexadiamine, triethylenediamine, N, N-dimethylbenzylamine, N, N-dimethylaniline, N, N-dimethyltoluidine, N, N-dimethylanisidine, pyridine, picoline, quinoline, N, N'-dimethylaminopyridine, N-methylpiperidine, N, N'-dimethylpiperazine, 1, 8-Diazabicyclo- [5,4, 0] -7-undecene (DBU) and the like.
- tertiary phosphines include trimethylphosphine, triethylphosphine, Examples include tripropylphosphine, tributylphosphine, triphenylphosphine, tris (p-tolyl) phosphine, dimethylphenylphosphine, and methyldiphenylphosphine.
- a hardening accelerator (C) can be suitably adjusted with the target hardening time etc., an above described epoxy resin (A), a phenol resin (B), and the said hardening accelerator (C).
- the range is preferably 0.01 to 2% by mass relative to the total mass.
- the epoxy resin composition of the present invention can use an organic solvent (hereinafter referred to as “organic solvent (D)”) in addition to the above-described components, depending on the intended use.
- organic solvent hereinafter referred to as “organic solvent (D)”
- the epoxy resin composition is used as a varnish for a copper clad laminate, the impregnation property to the base material is improved, and when it is used as an interlayer insulating material of a build-up printed circuit board, particularly as a build-up film, The coating property to the material sheet is improved.
- organic solvent (D) examples include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether
- ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
- the organic solvent (D) is used as a varnish for a copper clad laminate, it is preferable that the nonvolatile content in the composition is 50 to 70% by mass. On the other hand, when used as a varnish for a buildup film, the non-volatile content in the composition is preferably in the range of 30 to 60% by mass.
- the epoxy resin composition of the present invention may contain an inorganic filler, a modifier, a flame retardant, and the like as appropriate in addition to the components described above, depending on the intended use.
- Examples of the inorganic filler used here include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, magnesium hydroxide, and the like.
- the fused silica can be used in either crushed or spherical shape, but in order to increase the blending amount of the fused silica and to suppress the increase in the melt viscosity of the molding material, it is preferable to mainly use the spherical one. preferable. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica.
- the desired range of the blending ratio of the inorganic filler varies depending on the application and desired characteristics. For example, when used for a semiconductor sealing material, a higher ratio is preferable in view of the linear expansion coefficient and flame retardancy, and the epoxy resin composition It is preferably in the range of 65 to 95% by mass, particularly in the range of 85 to 95% by mass with respect to the total amount. Moreover, when using for uses, such as an electrically conductive paste and an electrically conductive film, electroconductive fillers, such as silver powder and copper powder, can be used.
- thermosetting resins and thermoplastic resins can be used as the modifier.
- phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether examples thereof include resins, polyphenylene sulfide resins, polyester resins, polystyrene resins, and polyethylene terephthalate resins.
- halogen compounds such as tetrabromobisphenol A type epoxy resin and brominated phenol novolak type epoxy resin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, Phosphate esters such as tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate, resorcin diphenyl phosphate, ammonium polyphosphate, Condensation of polyphosphate amide,
- Phosphorus atom-containing compounds such as phosphate ester compounds, nitrogen-containing compounds such as melamine, aluminum hydroxide, magnesium hydroxide, zinc borate, and inorganic flame retardant compounds such as calcium borate.
- the epoxy resin composition of the present invention is characterized by exhibiting an excellent flame retardant effect without using a halogen-based flame retardant having a high environmental load. It is preferable to use a phosphorus atom-containing compound, a nitrogen atom-containing compound, or an inorganic flame retardant compound.
- the conditions for thermosetting the epoxy resin composition of the present invention are not particularly limited, and can be cured under conditions for curing a normal phenol resin. Usually, it can carry out at the temperature of 120 to 250 degreeC. In particular, a temperature range of 150 to 220 ° C. is preferable from the viewpoint of good moldability.
- the epoxy resin composition of the present invention described in detail above is useful as a resin composition for copper-clad laminate, an interlayer insulating material for a build-up printed board, a build-up film, etc. It can also be used for a resin composition for a component sealing material, a resin composition for resist ink, a binder for friction material, a conductive paste, a resin casting material, an adhesive, a coating material such as an insulating paint, and the like.
- the method for producing a copper-clad laminate resin composition from the epoxy resin composition of the present invention specifically comprises the epoxy resin (A) and the phenol resin (B) as essential components, and further, if necessary, The method of mix
- the varnish preferably has a nonvolatile content in the range of 50 to 70% by mass from the viewpoint of impregnation into a fiber base material and prepreg productivity.
- the varnish obtained by the above method is impregnated into a fiber substrate such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ⁇ 170 ° C., a prepreg that is a cured product can be obtained.
- the blending ratio of the epoxy resin composition to be used and the reinforcing base is usually preferably adjusted so that the resin content in the prepreg is 20 to 60% by mass.
- the target copper-clad laminate can be obtained by laminating the obtained prepreg, and further stacking the copper foil and heat-pressing it.
- Specific examples of the method of thermocompression bonding include a method of performing a temperature condition of 170 to 250 ° C. under a pressure of 1 to 10 MPa. The thermocompression bonding is preferably performed for 10 minutes to 3 hours.
- the epoxy resin composition of the present invention is extremely useful as an interlayer insulating material for build-up printed circuit boards.
- the interlayer insulating material for such a build-up printed circuit board includes, in particular, the epoxy resin (A) and the phenol resin (B) as essential components, and further, if necessary, the organic solvent (D ) And a method of blending the curing accelerator (C).
- the varnish preferably has a nonvolatile content in the range of 30 to 60% by mass, particularly from the viewpoint of coating property and film formability.
- Specific examples of the method for producing a build-up substrate from the interlayer insulation material for a build-up substrate thus obtained include the following methods.
- the interlayer insulating material for a build-up substrate is applied to a wiring board on which a circuit is formed using a spray coating method, a curtain coating method, etc., and then cured, and then, if necessary, a predetermined through-hole portion or the like After drilling, the surface is treated with a roughening agent, and the surface is washed with hot water to form irregularities, and a metal such as copper is plated.
- the plating method is preferably electroless plating or electrolytic plating, and examples of the roughening agent include oxidizing agents, alkalis, and organic solvents.
- a build-up substrate can be obtained by alternately building up and forming a resin insulating layer and a conductor layer having a predetermined circuit pattern.
- the interlayer insulating material of the build-up printed circuit board can be used as a build-up film as well as the paint-like material described above.
- the epoxy resin composition of the present invention is particularly useful as a build-up film because the resin component itself exhibits excellent heat resistance.
- the method for producing a build-up film from the epoxy resin composition of the present invention includes, for example, a film for multilayer printed wiring board by coating the epoxy resin composition of the present invention on a support film to form a resin composition layer. The method of doing is mentioned.
- the film softens under the temperature condition of the laminate in the vacuum laminating method (usually 70 ° C. to 140 ° C.) and exists on the circuit board at the same time as the circuit board lamination. It is important to show fluidity (resin flow) that allows resin filling in the via hole or through hole to be formed, and it is preferable to blend the above-described components so as to exhibit such characteristics.
- the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. Usually, it is preferable that the resin can be filled in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.
- the method for producing the above-described film is prepared by preparing the varnish-like epoxy resin composition of the present invention, applying the varnish-like composition to the surface of the support film, and further heating or hot air.
- the organic solvent can be dried by spraying or the like to form an epoxy resin composition layer.
- the thickness of the formed layer is usually greater than or equal to the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 ⁇ m, the thickness of the resin composition layer is preferably 10 to 100 ⁇ m.
- the layer in this invention may be protected with the protective film mentioned later.
- a protective film By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.
- the above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil.
- the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.
- the thickness of the support film is not particularly limited, but is usually in the range of 10 to 150 ⁇ m, preferably in the range of 25 to 50 ⁇ m.
- the thickness of the protective film is preferably in the range of 1 to 40 ⁇ m.
- the support film described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film is peeled after the film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.
- a method for producing a multilayer printed wiring board using the film obtained as described above is, for example, when the layers are protected by a protective film, after peeling them, the layers are directly applied to the circuit board.
- Lamination is performed on one or both sides of the circuit board by, for example, vacuum laminating so as to come into contact.
- the laminating method may be a batch method or a continuous method using a roll. Further, the film and the circuit board may be heated (preheated) as necessary before lamination.
- the laminating conditions are a pressure bonding temperature (lamination temperature) of preferably 70 to 140 ° C. and a pressure bonding pressure of preferably 1 to 11 kgf / cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N / m 2 ). Lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.
- the passive component such as a capacitor and the active component such as an IC chip are placed in the substrate because of the characteristic of exhibiting excellent heat resistance in the present invention. It is particularly useful as an insulating material in a so-called embedded electronic component embedded substrate.
- the epoxy resin composition of the present invention exhibits excellent flame retardancy in a cured product, and is excellent in dielectric properties such as low dielectric loss tangent and low dielectric constant, and thus a resin composition for copper clad laminates, build It is useful as an interlayer insulation material for up-printed boards, build-up films, and the like.
- the epoxy resin composition of the present invention is used for other electronic component encapsulant resin compositions, resist ink resin compositions, friction material binders, conductive pastes, adhesives, insulating paints, resin casting materials, and the like. You can also.
- epoxy resin composition of the present invention is used as a resin composition for encapsulants of electronic components include semiconductor encapsulants, semiconductor tape encapsulants, potting liquid encapsulants, and underfill Examples thereof include resins and semiconductor interlayer insulating films.
- the epoxy resin composition of the present invention for a semiconductor sealing material, the epoxy resin (A), the phenol resin (B), other coupling agents blended as necessary, and a release agent.
- an additive such as an inorganic filler or the like may be premixed and then sufficiently mixed until uniform using an extruder, kneader, roll, or the like.
- the resin composition obtained by the above-mentioned method is heated to prepare a semi-cured sheet, which is used as a sealant tape, and then this sealant tape is used as a semiconductor. Examples include a method of placing on a chip, heating to 100 to 150 ° C. to soften and molding, and completely curing at 170 to 250 ° C.
- Examples of the method of using the epoxy resin composition of the present invention as a resist ink resin composition include, for example, the epoxy resin (A) and the phenol resin (B), an organic solvent (D), a pigment, talc, And a filler, and a composition for resist ink is applied to a printed circuit board by a screen printing method and then a resist ink cured product is used.
- Examples of the organic solvent (D) used here include methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, cyclohexanone, dimethyl sulfoxide, dimethylformamide, dioxolane, tetrahydrofuran, propylene glycol monomethyl ether acetate, ethyl lactate and the like. Is mentioned.
- a binder for a friction material in addition to the epoxy resin (A) and the phenol resin (B), formaldehyde is generated by heating with hexamethylenetetramine, paraformaldehyde and the like.
- a binder for a friction material can be produced by blending the curing accelerator (C) with a substance.
- a method of adding a filler, an additive and the like to each of the above components and thermally curing a method of impregnating each of the above components into a fiber substrate and thermosetting it Is mentioned.
- Fillers and additives used here are, for example, silica, barium sulfate, calcium carbonate, silicon carbide, cashew oil polymer, molybdenum disulfide, aluminum hydroxide, talc, clay, graphite, graphite, rubber particles, aluminum powder, copper Examples thereof include powder and brass powder.
- the resin composition obtained by the above-mentioned method is dissolved in a solvent as necessary, and then applied onto a semiconductor chip or an electronic component and directly cured. That's fine.
- the method of using the epoxy resin composition of the present invention as an underfill resin is, for example, by previously applying a varnish-like epoxy resin composition on a substrate or a semiconductor element, then semi-curing it, and heating to form a semiconductor element.
- a compression flow method in which the substrate is brought into close contact and completely cured can be used.
- the method of using the epoxy resin composition of the present invention as a semiconductor interlayer insulating material includes, for example, a curing accelerator (C) and a silane coupling agent in addition to the epoxy resin (A) and the phenol resin (B). Then, a method of preparing the composition and applying it on a silicon substrate by spin coating or the like can be mentioned.
- the linear expansion coefficient of the insulating material be close to the linear expansion coefficient of the semiconductor so that cracks due to the difference in linear expansion coefficient do not occur in a high temperature environment.
- a method for preparing a conductive paste from the epoxy resin composition of the present invention is, for example, a method in which fine conductive particles are dispersed in the epoxy resin composition to form a composition for an anisotropic conductive film, which is liquid at room temperature. And a paste resin composition for circuit connection and an anisotropic conductive adhesive.
- the method of adjusting the epoxy resin composition of the present invention to a resin composition for an adhesive is, for example, the epoxy resin (A), the phenol resin (B), if necessary, resins, a curing accelerator (C), Examples include a method of uniformly mixing solvents, additives, etc. using a mixing mixer or the like at room temperature or under heating. After applying to various base materials, the base material can be adhered by leaving it under heating. it can.
- the cured product of the present invention is obtained by molding and curing the epoxy resin composition of the present invention described in detail above, and is used as a laminate, cast product, adhesive, coating film, film, etc. depending on the application. it can. As described above, it is particularly useful as a copper clad laminate for a printed circuit board and a build-up film.
- Synthesis example 1 Add 883 parts of p-tertiary butylphenol, 88 parts of melamine, 253 parts of 41.5% formalin, and 1.8 parts of triethylamine to a flask equipped with a thermometer, condenser, fractionator, and stirrer. The temperature was gradually raised to 100 ° C. After reacting at 100 ° C. for 2 hours under reflux, the temperature was raised to 130 ° C. over 3 hours while removing water under normal pressure. Next, after making it react for 2 hours under recirculation
- phenol resin (B-1) A GPC chart of the resulting phenol resin (B-1) is shown in FIG. From the GPC chart, the content of the bifunctional compound represented by the structural formula (III) was 7.7%, and Mw / Mn was 1.56.
- Synthesis example 2 A phenol resin (B-2) was prepared in the same manner as in Synthesis Example 1, except that p-tertiary butylphenol was changed to 438 parts, melamine 63 parts, 41.5% formalin 106 parts, and triethylamine 1.8 parts in Synthesis Example 1. ) A GPC chart of the resulting phenol resin (B-2) is shown in FIG. From the GPC chart, the content of the bifunctional compound represented by the structural formula (III) was 8.4%, and Mw / Mn was 1.42.
- the phenol resin (X-1) was prepared in the same manner as in Synthesis Example 1 except that 630 parts of p-tertiary butylphenol and 1.3 parts of triethylamine in Synthesis Example 1 were changed to 395 parts of phenol and 0.8 part of triethylamine. Obtained.
- a GPC chart of the resulting phenol resin (X-1) is shown in FIG. From the GPC chart, the content of the bifunctional compound was 13.7%, and Mw / Mn was 2.02.
- Examples 3 to 4 and Comparative Example 3 An epoxy resin composition was prepared in the following manner, and a laminate and a film were prepared and subjected to various evaluation tests. The results are shown in Table 2.
- ⁇ Preparation of epoxy resin composition> For the cresol novolac type epoxy resin (“N-680” manufactured by DIC Corporation, epoxy group equivalent 212 g / equivalent), the number of hydroxyl groups of each phenol resin obtained in the synthesis example is one half of the number of moles of epoxy groups.
- Base material Polyethylene terephthalate film (thickness 38 ⁇ m) Film thickness: 40 ⁇ m Drying conditions: 100 ° C. Curing conditions: 5 hours at 180 ° C
- ⁇ Glass transition temperature> A cured product having a thickness of 0.8 mm was cut out from the laminate into a size of 5 mm in width and 54 mm in length, and this was used as a test piece. Using this test piece, a change in elastic modulus is maximized using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., Ltd., rectangular tension method: frequency 1 Hz, heating rate 3 ° C./min). The temperature (the highest tan ⁇ change rate) was evaluated as the glass transition temperature.
- DMA solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., Ltd., rectangular tension method: frequency 1 Hz, heating rate 3 ° C./min.
- the temperature (the highest tan ⁇ change rate) was evaluated as the glass transition temperature.
- the film was measured by a non-stationary hot wire method using a thermal conductivity meter “QTM-500” manufactured by Kyoto Electronics Co., Ltd.
- FIG. 2 is a GPC chart of the phenol resin (B-1) obtained in Synthesis Example 1.
- FIG. 4 is a GPC chart of a phenol resin (B-2) obtained in Synthesis Example 2.
- FIG. 2 is a GPC chart of a phenol resin (X-1) obtained in Comparative Synthesis Example 1.
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Abstract
Description
<エポキシ樹脂>
本発明の硬化性樹脂組成物に用いられるエポキシ樹脂(以下、「エポキシ樹脂(A)」とする。)について説明する。上記エポキシ樹脂(A)は、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールE型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ビスフェノールスルフィド型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂、ポリヒドロキシナフタレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ジシクロペンタジエン-フェノール付加反応型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフトール-フェノール共縮ノボラック型エポキシ樹脂、ナフトール-クレゾール共縮ノボラック型エポキシ樹脂、ビフェニル変性フェノール型エポキシ樹脂(フェノール骨格とビフェニル骨格がビスメチレン基で連結された他価フェノール型エポキシ樹脂)、ビフェニル変性ナフトール型エポキシ樹脂(ナフトール骨格とビフェニル骨格がビスメチレン基で連結された他価ナフトール型エポキシ樹脂)、アルコキシ基含有芳香環変性ノボラック型エポキシ樹脂(ホルムアルデヒドでグリシジル基含有芳香環及びアルコキシ基含有芳香環が連結された化合物)、フェニレンエーテル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂型エポキシ樹脂、キサンテン型エポキシ樹脂等が挙げられる。これらはそれぞれ単独で用いても良いし、2種以上を併用しても良い。
<GPC測定>
以下の条件により測定した。
測定装置 :東ソー株式会社製「HLC-8320 GPC」、
カラム:東ソー株式会社製ガードカラム「HXL-L」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G3000HXL」
+東ソー株式会社製「TSK-GEL G4000HXL」
検出器: RI(示差屈折)検出器
データ処理:東ソー株式会社製「EcoSEC-WS バージョン1.12」
測定条件: カラム温度 40℃
展開溶媒 テトラヒドロフラン
流速 1.0ml/分
標準 : 前記「EcoSEC-WS バージョン1.12」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
(使用ポリスチレン)
東ソー株式会社製「A-1000」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-20」
試料 : 樹脂固形分換算で1.0質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(50μl)。
下記構造式(I):
で表される構造部位βとを繰り返し構造単位として有するもの(Y)である。
したがって本発明は、エポキシ樹脂(A)及び前記(Y)を必須成分として含有するエポキシ樹脂組成物でもある。
上記した他の熱硬化性樹脂は、例えば、シアネートエステル樹脂、ベンゾオキサジン樹脂、マレイミド化合物、活性エステル樹脂、ビニルベンジル化合物、アクリル化合物、スチレンとマレイン酸無水物の共重合物などが挙げられる。上記した他の熱硬化性樹脂を併用する場合、その使用量は本発明の効果を阻害しなければ特に制限をうけないが、熱硬化性樹脂組成物100質量部中1~50重量部の範囲であることが好ましい。
前記シアネートエステル樹脂は、例えば、ビスフェノールA型シアネートエステル樹脂、ビスフェノールF型シアネートエステル樹脂、ビスフェノールE型シアネートエステル樹脂、ビスフェノールS型シアネートエステル樹脂、ビスフェノールM型シアネートエステル樹脂、ビスフェノールP型シアネートエステル樹脂、ビスフェノールZ型シアネートエステル樹脂、ビスフェノールAP型シアネートエステル樹脂、ビスフェノールスルフィド型シアネートエステル樹脂、フェニレンエーテル型シアネートエステル樹脂、ナフチレンエーテル型シアネートエステル樹脂、ビフェニル型シアネートエステル樹脂、テトラメチルビフェニル型シアネートエステル樹脂、ポリヒドロキシナフタレン型シアネートエステル樹脂、フェノールノボラック型シアネートエステル樹脂、クレゾールノボラック型シアネートエステル樹脂、トリフェニルメタン型シアネートエステル樹脂、テトラフェニルエタン型シアネートエステル樹脂、ジシクロペンタジエン-フェノール付加反応型シアネートエステル樹脂、フェノールアラルキル型シアネートエステル樹脂、ナフトールノボラック型シアネートエステル樹脂、ナフトールアラルキル型シアネートエステル樹脂、ナフトール-フェノール共縮ノボラック型シアネートエステル樹脂、ナフトール-クレゾール共縮ノボラック型シアネートエステル樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂型シアネートエステル樹脂、ビフェニル変性ノボラック型シアネートエステル樹脂、アントラセン型シアネートエステル樹脂等が挙げられる。これらはそれぞれ単独で用いても良いし、2種類以上を併用しても良い。
これらのシアネートエステル樹脂の中でも、特に耐熱性に優れる硬化物が得られる点においては、ビスフェノールA型シアネートエステル樹脂、ビスフェノールF型シアネートエステル樹脂、ビスフェノールE型シアネートエステル樹脂、ポリヒドロキシナフタレン型シアネートエステル樹脂、ナフチレンエーテル型シアネートエステル樹脂、ノボラック型シアネートエステル樹脂を用いることが好ましく、誘電特性に優れる硬化物が得られる点においては、ジシクロペンタジエン-フェノール付加反応型シアネートエステル樹脂が好ましい。
前記ベンゾオキサジン樹脂としては、特に制限はないが、例えば、ビスフェノールFとホルマリンとアニリンの反応生成物(F-a型ベンゾオキサジン樹脂)やジアミノジフェニルメタンとホルマリンとフェノールの反応生成物(P-d型ベンゾオキサジン樹脂)、ビスフェノールAとホルマリンとアニリンの反応生成物、ジヒドロキシジフェニルエーテルとホルマリンとアニリンの反応生成物、ジアミノジフェニルエーテルとホルマリンとフェノールの反応生成物、ジシクロペンタジエン-フェノール付加型樹脂とホルマリンとアニリンの反応生成物、フェノールフタレインとホルマリンとアニリンの反応生成物、ジフェニルスルフィドとホルマリンとアニリンの反応生成物などが挙げられる。これらはそれぞれ単独で用いても良いし、2種類以上を併用しても良い。
前記マレイミド化合物は、例えば、下記構造式(i)~(iii)の何れかで表される各種の化合物等が挙げられる。
活性エステル樹脂として、具体的にはジシクロペンタジエン-フェノール付加構造を含む活性エステル系樹脂、ナフタレン構造を含む活性エステル樹脂、フェノールノボラックのアセチル化物である活性エステル樹脂、フェノールノボラックのベンゾイル化物である活性エステル樹脂等が好ましく、なかでもピール強度の向上に優れるという点で、ジシクロペンタジエン-フェノール付加構造を含む活性エステル樹脂、ナフタレン構造を含む活性エステル樹脂がより好ましい。ジシクロペンタジエン-フェノール付加構造を含む活性エステル樹脂として、より具体的には下記一般式(iv):
本発明のエポキシ樹脂組成物は、エポキシ樹脂用硬化剤として前記フェノール樹脂(B)の他、本発明の効果を損なわない範囲でアミン系化合物、アミド系化合物、酸無水物系化合物、フェノ-ル系化合物など、その他のエポキシ樹脂用硬化剤(Z)を併用してもよい。この場合、該硬化剤(Z)は、前記フェノール樹脂(B)の一部を硬化剤(Z)に置き換えて使用することができる。即ち、硬化剤(Z)を併用する場合、該硬化剤(Z)中の活性水素と、フェノール樹脂(B)中の活性水素との合計が、エポキシ樹脂(A)中のエポキシ基1モルに対して、0.2~2となる割合であることが好ましい。また、硬化剤(Z)は、フェノール樹脂(B)との合計質量に対して、50質量%以下となる割合で使用することができる。
酸無水物系化合物は、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水マレイン酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸等が挙げられる。
-メチルイミダゾール、2-エチルイミダゾール、2,4-ジメチルイミダゾール、2-
ウンデシルイミダゾール、2-ヘプタデシルイミダゾール、2-フェニルイミダゾール、
2-フェニル-4-メチルイミダゾール、1-ベンジル-2-メチルイミダゾール、2-
フェニル-4,5-ジヒドロキシメチルイミダゾール、2-フェニル-4-メチル-5-
ヒドロキシメチルイミダゾール、1-ビニル-2-メチルイミダゾール、1-プロピル-
2-メチルイミダゾール、2-イソプロピルイミダゾール、1-シアノメチル-2-メチ
ル-イミダゾール、1-シアノエチル-2-エチル-4-メチルイミダゾール、1-シア
ノエチル-2-ウンデシルイミダゾール、1-シアノエチル-2-フェニルイミダゾール
等の他、マスク化イミダゾール類が挙げられる。
ルアミン、トリブチルアミン、テトラメチルブタンジアミン、テトラメチルペンタンジア
ミン、テトラメチルヘキサジアミン、トリエチレンジアミン、N,N-ジメチルベンジル
アミン、N,N-ジメチルアニリン、N,N-ジメチルトルイジン、N,N-ジメチルア
ニシジン、ピリジン、ピコリン、キノリン、N,N′-ジメチルアミノピリジン、N-メ
チルピペリジン、N,N′-ジメチルピペラジン、1,8-ジアザビシクロ-[5,4,
0]-7-ウンデセン(DBU)等が挙げられる。
トリプロピルホスフィン、トリブチルホスフィン、トリフェニルホスフィン、トリス(p-トリル)ホスフィン、ジメチルフェニルホスフィン、メチルジフェニルホスフィン等が挙げられる。
有機溶剤(D)の使用量は、銅張積層板用ワニスとして用いる場合、組成物中の不揮発分が50~70質量%となる範囲であることが好ましい。一方、ビルドアップフィルム用ワニスとして用いる場合、組成物中の不揮発分が30~60質量%となる範囲であることが好ましい。
<GPC測定>
以下の条件により測定した。
測定装置 :東ソー株式会社製「HLC-8320 GPC」、
カラム:東ソー株式会社製ガードカラム「HXL-L」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G2000HXL」
+東ソー株式会社製「TSK-GEL G3000HXL」
+東ソー株式会社製「TSK-GEL G4000HXL」
検出器: RI(示差屈折)検出器
データ処理:東ソー株式会社製「EcoSEC-WS バージョン1.12」
測定条件: カラム温度 40℃
展開溶媒 テトラヒドロフラン
流速 1.0ml/分
標準 : 前記「EcoSEC-WS バージョン1.12」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
(使用ポリスチレン)
東ソー株式会社製「A-1000」
東ソー株式会社製「A-5000」
東ソー株式会社製「F-2」
東ソー株式会社製「F-4」
東ソー株式会社製「F-20」
試料 : 樹脂固形分換算で1.0質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(50μl)。
温度計、冷却管、分留管、攪拌器を取り付けたフラスコに、p-ターシャリーブチルフェノール883部、メラミン88部、41.5%ホルマリン253部、およびトリエチルアミン1.8部を加え、発熱に注意しながら徐々に100℃まで昇温した。還流下100℃にて2時間反応させた後、常圧下にて水を除去しながら130℃まで3時間かけて昇温した。次に還流下にて2時間反応させた後、常圧下にて水を除去しながら150℃まで1時間かけて昇温した。さらに還流下で2時間反応させた後、常圧下にて水を除去しながら180℃まで2時間かけて昇温した。次に減圧下にて未反応のp-ターシャリーブチルフェノールを除去し、フェノール樹脂(B-1)を得た。得られたフェノール樹脂(B-1)のGPCチャートを図1に示す。GPCチャートより、構造式(III)で表される2官能性化合物の含有量は7.7%であり、Mw/Mnは1.56であった。
合成例1においてp-ターシャリーブチルフェノール438部、メラミン63部、41.5%ホルマリン106部、およびトリエチルアミン1.8部に変更した以外は合成例1と同様の操作で、フェノール樹脂(B-2)を得た。得られたフェノール樹脂(B-2)のGPCチャートを図2に示す。GPCチャートより、構造式(III)で表される2官能性化合物の含有量は8.4%であり、Mw/Mnは1.42であった。
合成例1のp-ターシャリーブチルフェノール630部、トリエチルアミン1.3部を、フェノール395部、トリエチルアミン0.8部に変更する以外は、合成例1と同様の操作でフェノール樹脂(X-1)を得た。得られたフェノール樹脂(X-1)のGPCチャートを図3に示す。GPCチャートより、2官能性化合物の含有量は13.7%であり、Mw/Mnは2.02であった。
合成例1のp-ターシャリーブチルフェノール630部、トリエチルアミン1.3部を、o-クレゾール454部、トリエチルアミン0.9部に変更する以外は、合成例1と同様の操作でフェノール樹脂(X-2)を得た。
下記要領で前記合成例及び比較合成例で得た各フェノール樹脂の溶剤溶解性を評価した。結果を表1に示す。
<溶剤溶解性試験>
不揮発分40、60質量%となるメチルエチルケトン(MEK)溶液、プロピレングリコールモノメチルエーテルアセテート(PMA)溶液を調製し、前記合成例及び比較合成例で得た各フェノール樹脂を入れたバイアルを室温で180日間放置し、不溶物が析出するまでの日数を比較した(値が大きい方が、溶剤溶解性が良好であることを示す。)表中の×は、加熱しても溶解しなかったことを表す。
下記要領でエポキシ樹脂組成物を調製し、積層板およびフィルムを作製して各種の評価試験を行った。結果を表2に示す。
<エポキシ樹脂組成物の調製>
クレゾールノボラック型エポキシ樹脂(DIC株式会社製「N-680」、エポキシ基当量212g/当量)に対し、合成例で得た各フェノール樹脂の水酸基数がエポキシ基のモル数の2分の1になるように両者を合計100gになるように配合し、2-エチル-4-メチルイミダゾール(四国化成工業株式会社製「2E4MZ」)をエポキシ樹脂とフェノール樹脂との合計質量に対し0.1質量%、球状アルミナ(平均粒径12.2μm)をエポキシ樹脂とフェノール樹脂との合計質量に対し20質量%加え、メチルエチルケトンで不揮発分を58質量%に調整して、エポキシ樹脂組成物を得た。
下記条件で積層板を作製した。
基材:日東紡績株式会社製 ガラスクロス「#2116」(210×280mm)
プライ数:6 プリプレグ化条件:160℃
硬化条件:200℃、40kg/cm2で1.5時間、成型後板厚:0.8mm
下記条件でフィルムを作製した。
膜厚:40μm 乾燥条件:100℃
硬化条件:180℃で5時間
積層板から厚さ0.8mmの硬化物を幅5mm、長さ54mmのサイズに切り出し、これを試験片とした。この試験片を粘弾性測定装置(DMA:レオメトリック社製固体粘弾性測定装置「RSAII」、レクタンギュラーテンション法:周波数1Hz、昇温速度3℃/分)を用いて、弾性率変化が最大となる(tanδ変化率が最も大きい)温度をガラス転移温度として評価した。
積層板を用いてJIS-C-6481に準拠し、アジレント・テクノロジー株式会社製ネットワークアナライザ「E8362C」を用い空洞共振法にて、絶乾後23℃、湿度50%の室内に24時間保管した後の試験片の1GHzでの誘電率および誘電正接を測定した。
積層板から厚さ0.8mmの硬化物を幅12.7mm、長さ127mmに切り出し、試験片とした。この試験片を用いてUL-94試験法に準拠し、試験片5本を用いて、燃焼試験を行った。
*1:試験片5本の合計燃焼時間(秒)
*2:1回の接炎における最大燃焼時間(秒)
フィルムを用いて京都電子株式会社製の熱導率計「QTM-500」を用い、非定常熱線法により測定した。
Claims (16)
- GPC測定から算出されるMw/Mnが1.35~1.85の範囲である請求項1記載のトリアジン環含有フェノール樹脂。
- 前記構造式(II)中のRがターシャリーブチル基である請求項1記載のトリアジン環含有フェノール樹脂。
- メラミン、パラ-アルキルフェノール、及びホルマリンを反応させることを特徴とするトリアジン環含有フェノール樹脂の製造方法。
- エポキシ樹脂(A)とフェノール樹脂(B)とを含有するエポキシ樹脂組成物であって、前記フェノール樹脂(B)として、請求項1~4の何れか一つに記載のトリアジン環含有フェノール樹脂を用いるエポキシ樹脂組成物。
- 更に、硬化促進剤を含有する請求項6記載のエポキシ樹脂組成物。
- 請求項6記載のエポキシ樹脂組成物を硬化してなる硬化物。
- 請求項6記載のエポキシ樹脂組成物を用いてなるプリプレグ。
- 請求項9記載のプリプレグを用いてなる回路基板。
- 請求項6記載のエポキシ樹脂組成物を用いてなるビルドアップフィルム。
- 請求項11記載のビルドアップフィルムを用いてなるビルドアップ基板。
- 請求項6記載のエポキシ樹脂組成物と、無機充填材とを含有する半導体封止材料。
- 請求項13記載の半導体封止材料を用いてなる半導体装置。
- 請求項6記載のエポキシ樹脂組成物と、強化繊維とを含有する繊維強化複合材料。
- 請求項15記載の繊維強化複合材料の硬化物である成形品。
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JP2016520088A JP6011745B2 (ja) | 2014-10-01 | 2015-09-24 | エポキシ樹脂組成物及びその硬化物 |
KR1020177004840A KR102332227B1 (ko) | 2014-10-01 | 2015-09-24 | 에폭시 수지 조성물 및 그 경화물 |
US15/512,637 US20170320994A1 (en) | 2014-10-01 | 2015-09-24 | Epoxy resin composition and cured product thereof |
CN201580053487.2A CN106795259B (zh) | 2014-10-01 | 2015-09-24 | 环氧树脂组合物及其固化物 |
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Cited By (3)
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WO2017209236A1 (ja) * | 2016-06-03 | 2017-12-07 | Dic株式会社 | 置換または非置換アリル基含有マレイミド化合物およびその製造方法、並びに前記化合物を用いた組成物および硬化物 |
US10035912B2 (en) * | 2015-11-04 | 2018-07-31 | Shin-Etsu Chemical Co., Ltd. | Flame retardant resin composition, flame retardant resin film, semiconductor device, and making method |
WO2018199306A1 (ja) * | 2017-04-28 | 2018-11-01 | 日立化成株式会社 | 封止用フィルム、封止構造体及び封止構造体の製造方法 |
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TWI626664B (zh) * | 2017-02-07 | 2018-06-11 | 聯茂電子股份有限公司 | 具有低介電損耗的無鹵素環氧樹脂組成物 |
TWI637405B (zh) * | 2017-03-15 | 2018-10-01 | 臻鼎科技股份有限公司 | 低介電樹脂組合物及應用其的膠片及電路板 |
CN107383341B (zh) * | 2017-07-11 | 2019-08-16 | 长木(宁波)新材料科技有限公司 | 一种水性环氧固化剂及其制备方法 |
CN108517715A (zh) * | 2018-04-03 | 2018-09-11 | 东华大学 | 一种纸蜂窝芯材浸渍料及其应用 |
US11541570B2 (en) * | 2019-01-07 | 2023-01-03 | Hi-Man Lee | Coating method of board for producing concrete product and board coated by same |
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- 2015-09-24 WO PCT/JP2015/076889 patent/WO2016052290A1/ja active Application Filing
- 2015-09-24 KR KR1020177004840A patent/KR102332227B1/ko active IP Right Grant
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US10035912B2 (en) * | 2015-11-04 | 2018-07-31 | Shin-Etsu Chemical Co., Ltd. | Flame retardant resin composition, flame retardant resin film, semiconductor device, and making method |
WO2017209236A1 (ja) * | 2016-06-03 | 2017-12-07 | Dic株式会社 | 置換または非置換アリル基含有マレイミド化合物およびその製造方法、並びに前記化合物を用いた組成物および硬化物 |
JPWO2017209236A1 (ja) * | 2016-06-03 | 2019-03-28 | Dic株式会社 | 置換または非置換アリル基含有マレイミド化合物およびその製造方法、並びに前記化合物を用いた組成物および硬化物 |
US10981865B2 (en) | 2016-06-03 | 2021-04-20 | Dic Corporation | Substituted or unsubstituted allyl group-containing maleimide compound, production method therefor, and composition and cured product using said compound |
WO2018199306A1 (ja) * | 2017-04-28 | 2018-11-01 | 日立化成株式会社 | 封止用フィルム、封止構造体及び封止構造体の製造方法 |
CN110546184A (zh) * | 2017-04-28 | 2019-12-06 | 日立化成株式会社 | 密封用膜、密封结构体和密封结构体的制造方法 |
KR20190139197A (ko) * | 2017-04-28 | 2019-12-17 | 히타치가세이가부시끼가이샤 | 봉지용 필름, 봉지 구조체 및 봉지 구조체의 제조 방법 |
JPWO2018199306A1 (ja) * | 2017-04-28 | 2020-03-12 | 日立化成株式会社 | 封止用フィルム、封止構造体及び封止構造体の製造方法 |
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CN110546184B (zh) * | 2017-04-28 | 2022-08-26 | 昭和电工材料株式会社 | 密封用膜、密封结构体和密封结构体的制造方法 |
KR102505321B1 (ko) * | 2017-04-28 | 2023-03-06 | 레조낙 가부시끼가이샤 | 봉지용 필름, 봉지 구조체 및 봉지 구조체의 제조 방법 |
Also Published As
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JPWO2016052290A1 (ja) | 2017-04-27 |
US20170320994A1 (en) | 2017-11-09 |
TW201627340A (zh) | 2016-08-01 |
JP6011745B2 (ja) | 2016-10-19 |
TWI670287B (zh) | 2019-09-01 |
CN106795259A (zh) | 2017-05-31 |
KR102332227B1 (ko) | 2021-11-29 |
CN106795259B (zh) | 2019-11-12 |
KR20170065489A (ko) | 2017-06-13 |
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