CN109071775B - Epoxy resin composition, curable composition, and semiconductor sealing material - Google Patents
Epoxy resin composition, curable composition, and semiconductor sealing material Download PDFInfo
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- CN109071775B CN109071775B CN201780021803.7A CN201780021803A CN109071775B CN 109071775 B CN109071775 B CN 109071775B CN 201780021803 A CN201780021803 A CN 201780021803A CN 109071775 B CN109071775 B CN 109071775B
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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Abstract
The invention provides a curable composition and a semiconductor sealing material which can obtain a cured product with excellent heat resistance and high quality retention rate when exposed to a high-temperature environment for a long time, and an epoxy resin composition used as a raw material of the curable composition and the semiconductor sealing material. Disclosed is an epoxy resin composition which is characterized by containing a novolak epoxy resin (A) and a diphenol epoxy resin (B), wherein a part or all of aromatic rings constituting a novolak structure of the novolak epoxy resin (A) has an aralkyl group.
Description
Technical Field
The present invention relates to a curable composition and a semiconductor sealing material that can provide a cured product having excellent heat resistance and high quality retention when exposed to a high-temperature environment for a long period of time, and an epoxy resin composition as a raw material for the curable composition and the semiconductor sealing material.
Background
Epoxy resins are used in materials such as adhesives, molding materials, and paints, and also widely used in the electrical and electronic fields such as semiconductor sealing materials and insulating materials for printed wiring boards because the resulting cured products are excellent in heat resistance, moisture resistance, and the like.
Among the various applications, in the field of semiconductor sealing materials, technological innovations such as the transfer to surface mount packages such as BGA and CSP, the handling of lead-free solder, and the elimination of halogen-based flame retardant materials are advancing, and specifically, resin materials that can achieve high flame retardancy even in the absence of halogen and further improve heat resistance and reduce the elastic modulus under heat are being sought. Further, since the semiconductor sealing material is used by filling a filler such as silica into a resin material, in order to increase the filling ratio, the resin material needs to have low viscosity and excellent fluidity in addition to the above-described properties.
As a resin material for coping with the above-described various required characteristics, for example, an epoxy resin composition is known which uses a mixture of a cresol novolac type epoxy resin, a 4, 4' -bisphenol type epoxy resin, and a brominated epoxy resin as a main component and a phenol aralkyl resin as a curing agent (see patent document 1 below).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2000-44775
The epoxy resin composition described in patent document 1 has high heat resistance evaluated at the glass transition temperature (Tg) of a cured product, but has a low mass retention rate when the cured product is exposed to a high-temperature environment for a long period of time, and cannot be said to have sufficient long-term use stability when used as a resin material for electronic devices and the like.
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide a curable composition and a semiconductor sealing material that can provide a cured product having excellent heat resistance and high quality retention when exposed to a high-temperature environment for a long period of time, and an epoxy resin composition as a raw material for the curable composition and the semiconductor sealing material.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that an epoxy resin material having a high quality retention rate when a cured product is exposed to a high-temperature environment for a long period of time can be formed by using a novolac-type epoxy resin having an aralkyl group introduced therein in combination with a biphenol-type epoxy resin, and have completed the present invention.
That is, the present invention relates to an epoxy resin composition containing a novolak type epoxy resin (a) and a biphenol type epoxy resin (B), wherein a part or all of aromatic rings constituting a novolak structure of the novolak type epoxy resin (a) have an aralkyl group.
The present invention also relates to a curable composition containing the epoxy resin composition and a curing agent.
The present invention also relates to a cured product of the curable composition.
The present invention also relates to a printed wiring board using the curable composition.
The present invention also relates to a semiconductor sealing material containing the epoxy resin composition, a curing agent, and an inorganic filler.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a curable composition and a semiconductor sealing material which can give a cured product having excellent heat resistance and a high quality retention rate when exposed to a high-temperature environment for a long period of time, and an epoxy resin composition as a raw material thereof.
Detailed Description
The present invention will be described in detail below.
The epoxy resin composition of the present invention is characterized by containing a novolak type epoxy resin (a) and a biphenol type epoxy resin (B), and the novolak type epoxy resin (a) has an aralkyl group in a part or all of aromatic rings constituting a novolak structure.
The ratio of the novolac epoxy resin (a) to the diphenol epoxy resin (B) may be appropriately adjusted depending on the desired melt viscosity, glass transition temperature (Tg), and the like, and the mass ratio [ (a)/(B) ] of the two is preferably in the range of 99/1 to 70/30, and more preferably in the range of 95/5 to 80/20, from the viewpoint of further improving the effect of obtaining a cured product having a high mass retention rate under high-temperature conditions.
Specifically, the novolak type epoxy resin (a) has a polyglycidyl ether of a novolak type resin which is a polycondensation product of a phenolic hydroxyl group-containing compound (x) and an aldehyde compound (y) as a main skeleton, and a part or all of aromatic rings constituting a novolak structure, that is, aromatic rings derived from the phenolic hydroxyl group-containing compound (x), have an aralkyl group.
Specific examples of the aralkyl group include a structural site represented by the following structural formula (1),
[ in the formula (1), R1Each independently represents any of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, Ar1Is any of phenyl, naphthyl, or a structural part having 1 or more halogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms on the aromatic nucleus thereof.]。
R in the aforementioned formula (1)1Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and the like. Among them, two R are preferable from the viewpoint of forming an epoxy resin having a high quality retention rate in a high-temperature environment1Are all hydrogen atoms.
Ar in the aforementioned formula (1)1Is any of phenyl, naphthyl, or a structural site having 1 or more halogen atoms and an alkyl group having 1 to 4 carbon atoms on the aromatic nucleus thereof. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group. Among them, phenyl group or naphthyl group is preferable from the viewpoint of forming an epoxy resin having a high quality retention rate in a high temperature environment.
The phenolic hydroxyl group-containing compound (x) is not particularly limited as long as it has a phenolic hydroxyl group in its molecular structure and can react with an aldehyde compound such as formaldehyde to produce a novolak type resin, and examples thereof include phenol, dihydroxybenzene, naphthol, dihydroxynaphthalene, anthraphenol, and compounds having one or more substituents such as a halogen atom, an alkyl group, and an alkoxy group on their aromatic nucleus. These may be used alone or in combination of 2 or more. Among them, phenol, naphthol, and a compound having one or more halogen atoms, alkyl groups, alkoxy groups, or the like in the aromatic nucleus thereof are preferable, phenol, naphthol, and a compound having 1 or 2 alkyl groups in the aromatic nucleus thereof are more preferable, and phenol or cresol is particularly preferable, from the viewpoint of forming an epoxy resin composition having an excellent balance between heat resistance and curability of a cured product.
Examples of the aldehyde compound (y) include alkyl aldehydes such as formaldehyde and acetaldehyde, and aromatic aldehydes such as benzaldehyde. These may be used alone or in combination of 2 or more. Among these, formaldehyde is preferred in view of forming an epoxy resin composition having an excellent balance between heat resistance and curability of a cured product. Formaldehyde can be used in the form of formalin solution or in the form of paraformaldehyde.
The method for producing the novolak type epoxy resin (a) is not particularly limited, and examples thereof include: a method (method 1) of obtaining a polyglycidyl ether of a novolak-type resin which is a polycondensate of a phenolic hydroxyl group-containing compound (x) and an aldehyde compound (y), and reacting the polyglycidyl ether with an aralkylating agent (z); a method (method 2) in which a novolak resin that is a polycondensate of a phenolic hydroxyl group-containing compound (x) and an aldehyde compound (y) is reacted with an aralkylating agent (z) to obtain an aralkyl-modified novolak resin (a), and the aralkyl-modified novolak resin is subjected to polyglycidyl etherification; a method (method 3) in which a partial or whole of the phenolic hydroxyl group-containing compound (x) is reacted with an aralkylating agent (z) to thereby carry out polyglycidyl etherification of a polycondensate thereof with the aldehyde compound (y). Among them, the above-mentioned method 2 is preferable in view of easy control of the reaction.
The method 2 will be explained. The reaction of the phenolic hydroxyl group-containing compound (x) with the aldehyde compound (y) may be carried out, for example, by using an acid catalyst as a polymerization catalyst at a temperature of 100 to 200 ℃. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, and lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. These may be used alone or in combination of 2 or more. The amount of the acid catalyst used is preferably in the range of 0.1 to 5% by mass based on the total mass of the reaction raw materials.
The ratio of the reaction between the phenolic hydroxyl group-containing compound (x) and the aldehyde compound (y) is preferably in the range of 0.01 to 0.9 mol based on 1 mol of the phenolic hydroxyl group-containing compound (x), from the viewpoint of easy control of the reaction.
The reaction of the phenolic hydroxyl group-containing compound (x) with the aldehyde compound (y) may be carried out in an organic solvent as required. The organic solvent used here is not particularly limited as long as it can be used under the above temperature conditions, and specific examples thereof include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. When these organic solvents are used, they are preferably used in a range of 10 to 500 mass% with respect to the total mass of the reaction raw materials.
In the reaction of the phenolic hydroxyl group-containing compound (x) and the aldehyde compound (y), various antioxidants and reducing agents can be used for the purpose of suppressing the coloration of the resulting novolak resin. Examples of the antioxidant include hindered phenol compounds such as 2, 6-dialkylphenol derivatives, 2-valent sulfur compounds, and phosphite compounds containing 3-valent phosphorus atoms. Examples of the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, dithionite (hydrosulfite), salts thereof, and zinc.
After the reaction, the reaction mixture is neutralized or washed with water, and unreacted reaction materials, by-products, and the like are distilled off to obtain a novolak type resin as an intermediate.
Subsequently, the novolak type resin obtained is reacted with an aralkylating agent (z). The aralkylating agent (z) is not particularly limited as long as it is a compound capable of introducing an aralkyl group into the aromatic ring of the novolak resin, and any compound may be used. Among them, preferred compounds are those represented by any of the following structural formulae (3-1) to (3-3) because of their high reactivity and the like,
[ in the formula, X represents a halogen atom. R1Each independently represents any of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, Ar1Is any of phenyl, naphthyl, or a structural part having 1 or more halogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms on the aromatic nucleus thereof.]. These aralkylating agents (z) may be used alone or in combination of 2 or more.
Among the compounds represented by any of the structural formulae (3-1) to (3-3), the compound represented by the structural formula (3-1) is preferable, and Ar in the formula is more preferable, from the viewpoint of high reactivity1A compound that is phenyl or naphthyl.
The reaction between the novolak type resin and the aralkylating agent (z) may be carried out in the presence of an acid catalyst at a temperature of 100 to 200 ℃. The reaction temperature is more preferably 130 ℃ or higher, and still more preferably 130 ℃ or higher for 4 hours or longer, from the viewpoint of promoting the production of the aralkylated product (. alpha.) described later.
Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, and lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. These may be used alone or in combination of 2 or more. The amount of the acid catalyst used is preferably in the range of 0.1 to 5% by mass based on the total mass of the reaction raw materials.
The reaction ratio of the novolak type resin and the aralkylating agent (z) is preferably 0.25 to 0.80 mol based on 1 mol of the phenolic hydroxyl group-containing compound (x), from the viewpoint of forming an epoxy resin composition having a high mass retention under a high-temperature environment.
The reaction between the novolak type resin and the aralkylating agent (z) may be carried out in an organic solvent as required. The organic solvent used here is not particularly limited as long as it can be used under the above temperature conditions, and specific examples thereof include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. When these organic solvents are used, they are preferably used in a range of 10 to 500 mass% with respect to the total mass of the reaction raw materials.
After the reaction, the reaction solution may be used as it is to perform the polyglycidyl etherification step, or the reaction product may be neutralized or washed with water and then subjected to the polyglycidyl etherification step.
The hydroxyl group equivalent of the obtained aralkyl-modified novolak resin (a) is preferably in the range of 200 to 270 g/equivalent in view of forming an epoxy resin composition having a high mass retention rate in a high-temperature environment.
Examples of the polyglycidyl etherification step of the aralkyl-modified novolak resin (a) include the following steps: the reaction is carried out at a temperature of 20 to 120 ℃ for 0.5 to 10 hours using 2 to 10 moles of epihalohydrin per 1 mole of hydroxyl groups of the aralkyl-modified novolak resin (a) while adding 0.9 to 2.0 moles of a basic catalyst to 1 mole of phenolic hydroxyl groups at a time or in portions.
Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. Among them, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity, and specifically, sodium hydroxide, potassium hydroxide, and the like are preferable.
In the case of industrial production, it is preferable that all of the epihalohydrins used in the charge are new in the first batch of the production of the epoxy resin, and that the epihalohydrin recovered from the crude reaction product and new epihalohydrin corresponding to the lost part which is consumed in the reaction are used in combination after the next batch. In this case, the epihalohydrin to be used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β -methylepichlorohydrin, and the like. Among them, epichlorohydrin is preferable in terms of easy industrial availability.
The reaction of the aralkyl-modified novolak resin (a) with epihalohydrin can be accelerated by carrying out the reaction in an organic solvent. Examples of the organic solvent used here include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbon solvents such as toluene and xylene, alcoholic solvents such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, sec-butanol and tert-butanol, cellosolve solvents such as methyl cellosolve and ethyl cellosolve, ether solvents such as tetrahydrofuran, 1, 4-dioxane, 1, 3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of 2 or more.
After the reaction, the reaction mixture was washed with water, and then, unreacted epihalohydrin and the organic solvent were distilled off by heating and distillation under reduced pressure. In order to produce an epoxy resin having less hydrolyzable halogen, the obtained epoxy resin may be dissolved again in an organic solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added to the solution to further react the resin. At this time, a quaternary ammonium salt, crown ether or the like may be present for the purpose of increasing the reaction rate. The amount of the phase transfer catalyst used is preferably 0.1 to 3.0 parts by mass per 100 parts by mass of the epoxy resin. After the reaction is completed, the formed salt is removed by filtration, washing with water, or the like, and the organic solvent is distilled off under reduced pressure and heating, thereby obtaining the objective novolak-type epoxy resin (a).
The novolac epoxy resin (a) is preferably an aralkylated product (α) containing a glycidyl ether of a phenolic hydroxyl group-containing compound (x) from the viewpoint of forming an epoxy resin composition which is excellent in heat resistance of a cured product, has a high mass retention rate in a high-temperature environment, and further has high fluidity. When the phenolic hydroxyl group-containing compound (x) is any of phenol, naphthol, and a compound having 1 or 2 alkyl groups on the aromatic nucleus thereof, the aralkylated product (. alpha.) is specifically a compound having a molecular structure represented by the following formula (2-1) or (2-2),
[ in the formula, R1Each independently represents any of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, Ar1Is any of phenyl, naphthyl or structural sites having 1 or more halogen atoms and alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus thereof, and m is 1 or 2. R2Each independently is any one of alkyl groups having 1 to 4 carbon atoms, and n is 0, 1 or 2.]。
The epoxy resin composition of the present invention contains the diphenol type epoxy resin (B) as an essential component together with the novolak type epoxy resin (a). Specifically, the biphenol-type epoxy resin (B) is a resin obtained by polyglycidyl etherification of a phenol hydroxyl group-containing compound (B) having a biphenol skeleton, and examples of the phenol hydroxyl group-containing compound (B) having a biphenol skeleton include compounds represented by the following structural formula (4),
(in the formula, R3Each independently is any one of alkyl groups having 1 to 4 carbon atoms, and p is 0, 1 or 2. ). The phenolic hydroxyl group-containing compounds (b) having a biphenol skeleton may be used singly or in combination of 2 or more.
Among the compounds represented by the structural formula (4), 4 '-biphenol-type compounds having two hydroxyl groups bonded to the 4-position and the 4' -position are preferable in that an epoxy resin composition having a high quality retention rate in a high-temperature environment can be obtained.
The polyglycidyl etherification of the phenolic hydroxyl group-containing compound (b) having a biphenol skeleton can be carried out by the same method as the polyglycidyl etherification of the aralkyl modified novolak-type resin (a) described in detail in the production of the novolak-type epoxy resin (A).
The epoxy resin composition of the present invention may contain another epoxy resin (C) in addition to the novolak epoxy resin (a) and the diphenol epoxy resin (B). In the case where the other epoxy resin (C) is contained, the total amount of the novolac-type epoxy resin (a) and the diphenol-type epoxy resin (B) is preferably 50% by mass or more, and preferably 80% by mass or more, based on the total mass of the epoxy resins, from the viewpoint that the effect of obtaining a cured product having a high mass retention under high-temperature conditions is further improved.
Examples of the other epoxy resin (C) include naphthalene skeleton-containing epoxy resins such as diglycidyl ether oxynaphthalene, naphthol novolac-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, and 1, 1-bis (2, 7-diglycidyl ether oxy-1-naphthyl) alkane; bisphenol epoxy resins such as bisphenol a epoxy resin and bisphenol F epoxy resin; novolac-type epoxy resins such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol a novolac-type epoxy resins, epoxides of condensates of phenolic compounds and aromatic aldehydes having phenolic hydroxyl groups, and biphenol novolac-type epoxy resins; triphenylmethane type epoxy resins; tetraphenylethane type epoxy resins; dicyclopentadiene-phenol addition reaction type epoxy resin; epoxy resins containing phosphorus atoms, and the like.
The epoxy resin composition of the present invention can be produced by a method of producing and mixing the novolac epoxy resin (a), the diphenol epoxy resin (B), and the other epoxy resin (C) used as needed. Alternatively, an epoxy resin composition containing the novolak epoxy resin (a), the diphenol epoxy resin (B) and, if necessary, another epoxy resin (C) may be produced by previously mixing the novolak resin precursors of the respective epoxy resins and subjecting the mixture to polyglycidyl etherification. The polyglycidyl etherification step here can be carried out by the same method as that for the polyglycidyl etherification of the aralkyl modified novolak resin (a) described in detail in the production of the novolak epoxy resin (a).
In the case of producing an epoxy resin composition by the latter method, the compounding ratio of the aralkyl modified novolak type resin (a) which is a precursor of the novolak type epoxy resin (a) to the phenolic hydroxyl group-containing compound (b) having a diphenol skeleton is preferably in the range of 99/1 to 70/30, more preferably in the range of 99/1 to 80/20 in terms of further improving the effect of obtaining a cured product having a high mass retention rate under high temperature conditions.
When the epoxy resin composition contains the other epoxy resin (C), the total amount of the aralkyl modified novolac resin (a) and the phenolic hydroxyl group-containing compound (b) having a biphenol skeleton is preferably 50% by mass or more, and more preferably 80% by mass or more, based on the total mass of the aralkyl modified novolac resin (a), the phenolic hydroxyl group-containing compound (b) having a biphenol skeleton, and the phenolic resin precursor (C) of the other epoxy resin (C).
The epoxy resin composition of the present invention preferably has an epoxy equivalent ranging from 200 to 270 g/equivalent. The melt viscosity of the epoxy resin composition of the present invention is preferably in the range of 0.01 to 3 dPas measured at 150 ℃.
The curable composition of the present invention contains the above-described epoxy resin composition and the curing agent as essential components.
Examples of the curing agent used herein include amine compounds, amide compounds, acid anhydrides, phenol resins, and the like, and these may be used alone or in combination of two or more. Examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, and BF3Amine complexes, guanidine derivatives, etc. Examples of the amide compound include dicyandiamide, aliphatic dibasic acids, dimer acids, polyamide resins synthesized from carboxylic acid compounds of fatty acids and amines such as ethylenediamine, and the like. Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and maleic anhydrideAcid anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like. Examples of the phenol resin include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition-type resins, phenol aralkyl resins (Xylock resins), polyhydric phenol novolac resins synthesized from a polyhydric hydroxyl compound and formaldehyde, such as resorcinol novolac resins, naphthol aralkyl resins, trimethylolmethane resins, tetrahydroxyphenyl ethane resins, naphthol novolac resins, naphthol-phenol cocondensed novolac resins, naphthol-cresol cocondensed novolac resins, biphenyl-modified phenol resins (polyhydric phenol compounds in which phenol cores are connected by dimethylene), biphenyl-modified naphthol resins (polyhydric naphthol compounds in which phenol cores are connected by dimethylene), aminotriazine-modified phenol resins (polyhydric phenol compounds in which phenol cores are connected by melamine, benzoguanamine, or the like), and the like, And polyphenol compounds such as alkoxy group-containing aromatic ring-modified novolak resins (polyphenol compounds obtained by linking a phenol core and an alkoxy group-containing aromatic ring with formaldehyde). These may be used alone or in combination of 2 or more.
In the curable composition of the present invention, the compounding ratio of the epoxy resin composition and the curing agent is preferably such that the active group in the curing agent is in an amount of 0.7 to 1.5 equivalents relative to 1 equivalent of the total of epoxy groups in the epoxy resin composition, from the viewpoint of excellent curability and obtaining a cured product excellent in heat resistance and toughness.
The curable composition of the present invention may further contain an allyl group-containing resin represented by cyanate ester resin, bismaleimide resin, benzoxazine resin, styrene-maleic anhydride resin, diallyl bisphenol, triallyl isocyanurate, polyphosphate ester, phosphate ester-carbonate copolymer, or the like. These may be used alone or in combination of 2 or more.
The curable composition of the present invention may contain various additives such as a curing accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.
Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, lewis acids, and amine complex salts. Among them, 2-ethyl-4-methylimidazole is preferable as the imidazole compound, triphenylphosphine is preferable as the phosphorus compound, and 1, 8-diazabicyclo- [5.4.0] -undecene (DBU) is preferable as the tertiary amine, from the viewpoint of excellent curability, heat resistance, electrical characteristics, moisture resistance reliability, and the like.
Examples of the flame retardant include inorganic phosphorus compounds such as ammonium phosphates and phosphoric acid amides, e.g., red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; organic phosphorus compounds such as phosphate compounds, phosphonic acid compounds, hypophosphorous acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives thereof obtained by reacting these compounds with compounds such as epoxy resins and phenol resins; nitrogen flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine, and the like; silicone flame retardants such as silicone oil, silicone rubber, and silicone resin; inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. When these flame retardants are used, the amount of the flame retardants is preferably in the range of 0.1 to 20% by mass in the curable composition.
The inorganic filler is added, for example, when the curable composition of the present invention is used for a semiconductor sealing material. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among these, the fused silica is preferable in that an inorganic filler can be added in a larger amount. The fused silica may be used in a crushed form or a spherical form, and it is preferable to mainly use the spherical fused silica in order to increase the amount of the fused silica to be mixed and to suppress an increase in melt viscosity of the curable composition. Further, in order to increase the amount of the spherical silica to be blended, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling ratio is preferably in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable composition.
When the curable composition of the present invention is used for applications such as a conductive paste, a conductive filler such as silver powder or copper powder can be used.
The curable composition of the present invention is obtained by uniformly mixing the above components. The curable composition of the present invention, which is obtained by blending an epoxy resin component, a curing agent and, if necessary, a curing accelerator, can be easily prepared into a cured product by the same method as a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast molded products, adhesive layers, coating films, and films.
When the curable composition of the present invention is used for printed circuit boards and build-up adhesive films, it is preferable to add an organic solvent. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol ethyl ether acetate (ethylene glycol methyl ether acetate), and propylene glycol methyl ether acetate. The type and amount of the organic solvent may be suitably adjusted depending on the use environment of the curable composition, and for example, in the case of printed wiring board use, a polar solvent having a boiling point of 160 ℃ or less such as methyl ethyl ketone, acetone, or dimethylformamide is preferably used in a proportion such that the nonvolatile content is 40 to 80 mass%. For the use of the build-up adhesive film, it is preferable to use a ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone, an acetate solvent such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, a carbitol solvent such as cellosolve, butyl carbitol, an aromatic hydrocarbon solvent such as toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and it is preferable to use them in such a proportion that the nonvolatile content is 30 to 60 mass%.
Further, examples of the method for producing a printed circuit board using the curable composition of the present invention include the following methods: a prepreg is obtained by impregnating a reinforcing base material with a varnish-like curable composition containing an epoxy resin composition, a curing agent, an organic solvent, other additives, and the like, curing the composition, and then laminating the prepreg with a copper foil and heating and pressure bonding the laminate. Examples of the reinforcing base material include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The impregnation amount of the curable composition is not particularly limited, and it is usually preferably prepared so that the resin component in the prepreg is 20 to 60 mass%.
When the curable composition of the present invention is used for applications as a semiconductor sealing material, the semiconductor sealing material can be obtained by a method in which a compound such as an epoxy resin composition, a curing agent, and a filler is sufficiently mixed until the mixture becomes uniform, for example, by an extruder, a kneader, a roll, or the like. The filler used here includes the aforementioned inorganic filler, and is preferably used in a range of 0.5 to 95 parts by mass per 100 parts by mass of the curable composition, as described above. Among them, from the viewpoint of improving flame retardancy, moisture resistance, solder crack resistance and reducing the linear expansion coefficient, it is preferably used in the range of 70 to 95 parts by mass, and particularly preferably used in the range of 80 to 95 parts by mass.
The method for molding a semiconductor package using the obtained semiconductor sealing material includes, for example, a method of molding the semiconductor sealing material by a cast molding machine, a transfer molding machine, an injection molding machine or the like, and further heating the molded product at a temperature of 50 to 200 ℃ for 2 to 10 hours, and a semiconductor device as a molded product can be obtained by such a method.
[ examples ]
The present invention will be described specifically with reference to examples and comparative examples, and the following "parts" and "%" are based on mass unless otherwise specified. The epoxy equivalent, the melt viscosity at 150 ℃, GPC, and MS spectrum were measured under the following conditions.
Measurement of epoxy equivalent
Measured according to JIS K7236.
Measurement of melt viscosity at 150 ℃ C
Measurements were made with an ICI viscometer based on ASTM D4287.
Measurement of softening Point
Measured according to JIS K7234.
MS Spectrum measurement conditions
Double focusing type mass spectrometer "AX 505H (FD 505H)" manufactured by Nippon electronic Co., Ltd "
PREPARATION EXAMPLE 1 preparation of aralkyl-modified novolak type resin (a-1)
A flask equipped with a thermometer, a condenser, a fractionating tube, a nitrogen inlet tube, and a stirrer was charged with 216.3g of o-cresol and 14.5g of 41 mass% formalin, and 4.0g of oxalic acid was added thereto. The temperature was raised to 100 ℃ and the reaction was carried out at 100 ℃ for 3 hours. Then, 76.7g of 41 mass% formalin was added dropwise over 1 hour while trapping water in a fractionating tube. After the completion of the dropwise addition, the temperature was raised to 150 ℃ over 1 hour, and the reaction was further carried out at 150 ℃ for 2 hours. After the reaction, 600g of methyl isobutyl ketone was further added, and the mixture was transferred to a separatory funnel and washed with water. After washing with water until the washing water became neutral, unreacted o-cresol and methyl isobutyl ketone were distilled off from the organic layer under heating and reduced pressure to obtain 190g of a novolak type resin intermediate. The novolak-type resin intermediate obtained had a hydroxyl equivalent of 117 g/equivalent and a softening point of 64 ℃.
Subsequently, 117g of the novolak type resin intermediate obtained in the previous step, 71g of benzyl alcohol, 2g of p-toluenesulfonic acid and 117g of xylene were put into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, and the temperature was raised from room temperature to 140 ℃ while stirring. The reaction was carried out at 140 ℃ for 4 hours, and the temperature was raised to 150 ℃ for 3 hours. After the reaction, the temperature was reduced to 80 ℃ and 1g of 49% sodium hydroxide was added to neutralize the reaction mixture. The resin was dried under reduced pressure and heating to obtain 150 parts by mass of an aralkyl-modified novolak resin (a-1). The hydroxyl group equivalent of the obtained aralkyl-modified novolak resin (a-1) was 181 g/equivalent.
EXAMPLE 1 production of epoxy resin composition (1)
In a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, 148.5g of the obtained aralkyl modified novolak type resin (a-1), 16.5g of 4, 4' -biphenol, 463g of epichlorohydrin, 139g of n-butanol and 2g of tetraethylbenzyl ammonium chloride were charged and dissolved while purging with nitrogen. After the temperature was raised to 70 ℃ 220g of a 20% aqueous solution of sodium hydroxide was added dropwise over 5 hours, and the mixture was further stirred at the same temperature for 0.5 hour. Unreacted epichlorohydrin was distilled off by distillation under reduced pressure, and 1000g of methyl isobutyl ketone and 350g of n-butanol were added to dissolve the product. To the solution was added 10g of a 10% aqueous sodium hydroxide solution, and the mixture was reacted at 80 ℃ for 2 hours. After the reaction, washing with 150g of water was repeated 3 times to confirm that the pH of the washing solution was neutral. Then, the inside of the system was dehydrated by azeotropy, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 235g of the objective epoxy resin composition (1). The obtained epoxy resin composition (1) had a melt viscosity of 0.8 dPas, a softening point of 90 ℃ and an epoxy equivalent of 255 g/eq. By MS spectrum analysis, the formation of the compound represented by the following structural formula (5) and the compound represented by the following structural formula (6) was confirmed.
EXAMPLE 2 production of epoxy resin composition (2)
In a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, 164.4g of the aralkyl-modified novolak resin (a-1) obtained in the previous step, 8.7g of 4, 4' -biphenol, 463g of epichlorohydrin, 139g of n-butanol and 2g of tetraethylbenzyl ammonium chloride were charged and dissolved while purging with nitrogen. After the temperature was raised to 70 ℃ 220g of a 20% aqueous solution of sodium hydroxide was added dropwise over 5 hours, and the mixture was further stirred at the same temperature for 0.5 hour. Unreacted epichlorohydrin was distilled off by distillation under reduced pressure, and 1000g of methyl isobutyl ketone and 350g of n-butanol were added to dissolve the product. To the solution was added 10g of a 10% aqueous sodium hydroxide solution, and the mixture was reacted at 80 ℃ for 2 hours. After the reaction, washing with 150g of water was repeated 3 times to confirm that the pH of the washing solution was neutral. Then, the inside of the system was dehydrated by azeotropy, followed by microfiltration, and then the solvent was distilled off under reduced pressure to obtain 231g of the objective epoxy resin composition (2). The obtained epoxy resin composition (2) had a melt viscosity of 0.9 dPas, a softening point of 73 ℃ and an epoxy equivalent of 260 g/equivalent. The formation of the compound represented by the structural formula (5) and the compound represented by the structural formula (6) was confirmed by MS spectrum analysis.
Comparative production example 1 production of epoxy resin (1')
An epoxy resin (1 ') 150g was obtained in the same manner as in example 1 except that 90.6g of an o-cresol novolak resin ("KA-1160", manufactured by DIC corporation) and 22.8g of 4,4 ' -biphenol were used in place of 148.5g of the aralkyl modified novolak resin (a-1) and 16.5g of 4,4 ' -biphenol in example 1. The resulting epoxy resin (1') had a melt viscosity of 1.0 dPas and an epoxy equivalent of 195 g/eq.
Examples 3 and 4 and comparative example 1
The curable composition and the test piece were prepared in the following manner, and heat resistance and quality retention under high temperature conditions were evaluated. The evaluation results are shown in table 1.
Preparation of curable composition
The components were compounded in accordance with the composition shown in Table 1, and melt-kneaded with 2 rolls at a temperature of 90 ℃ for 5 minutes to obtain a curable composition. The details of each component are as follows.
Curing agent: phenol novolak type phenol resin (TD-2131, manufactured by DIC K.K.; hydroxyl equivalent 104g/eq)
Curing accelerator: triphenylphosphine
Fused silica: FB-560 manufactured by electrochemistry corporation "
Silane coupling agent: gamma-glycidoxypropyltrimethoxysilane (KBM-403, product of shin-Etsu chemical Co., Ltd.)
Carnauba wax: CERARICA NODA Co., Ltd. "PEARL WAX No. 1-P" manufactured by Ltd "
Production of test piece
Pulverizing the curable composition, and transfer moldingMachine under a pressure of 70kg/cm2The plate was pressed at a press speed of 5 cm/sec at a temperature of 175 ℃ for 180 seconds to form a rectangular plate having a width of 12.7mm, a length of 127mm and a thickness of 1.6mm, to obtain a test piece.
Evaluation of Heat resistance
A sample cut out from the test piece to a size of 5 mm. times.54 mm. times.2.4 mm was measured for a glass transition temperature (Tg) at a temperature at which the change in elastic modulus was maximized (tan. delta. change rate was maximized) using a viscoelasticity measuring apparatus ("solid viscoelasticity measuring apparatus RSAII" manufactured by Rheometric Co., Ltd., rectangular drawing method; frequency 1Hz, temperature rise rate 3 ℃/min).
Mass retention under high temperature conditions
A sample cut out to a size of 5 mm. times.54 mm. times.2.4 mm from the aforementioned test piece was left to stand at a temperature of 250 ℃ for 1000 hours. The mass retention rate was evaluated as [ mass of test piece after test/mass of test piece before test ] × 100 (%).
[ Table 1]
| TABLE 1 | Example 3 | Example 4 | Comparative example 1 |
| Epoxy resin composition (1) [ parts by mass] | 93 | ||
| Epoxy resin composition (2) [ parts by mass] | 94 | ||
| Epoxy resin (1') [ parts by mass] | 85 | ||
| Curing agent [ parts by mass] | 38 | 37 | 46 |
| Curing Accelerator [ parts by mass] | 3 | 3 | 3 |
| Fused silica [ parts by mass] | 86 | 86 | 86 |
| Silane coupling agent [ parts by mass] | 2 | 2 | 2 |
| Carnauba wax [ parts by mass] | 1 | 1 | 1 |
| Carbon Black [ parts by mass] | 3 | 3 | 3 |
| Heat resistance (Tg) [. degree C] | ＞130 | ＞130 | ＞130 |
| Mass retention rate under high temperature conditions [% ]] | 98.3 | 97.9 | 95.4 |
Claims (8)
1. An epoxy resin composition comprising a novolak epoxy resin (A) having an aralkyl group in a part or all of aromatic rings constituting a novolak structure and a biphenol epoxy resin (B) which is a polyglycidyl ether of 4, 4' -biphenol,
the epoxy resin composition contains: an aralkylated product (. alpha.) of a glycidyl ether of the phenolic hydroxyl group-containing compound (x),
the phenolic hydroxyl group-containing compound (x) as a raw material of the novolak epoxy resin (A) is any of phenol, naphthol, and a compound having 1 or 2 alkyl groups on the aromatic nucleus thereof, and the aralkylated product (. alpha.) is a compound having a molecular structure represented by the following structural formula (2-1) or (2-2),
in the formulae (2-1) and (2-2), R1Each independently represents any of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, Ar1Is any of phenyl, naphthyl or structural sites having 1 or more halogen atoms and alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus thereof, m is 1 or 2, R2Each independently is any one of alkyl groups having 1 to 4 carbon atoms, n is 0, 1 or 2, and G is a glycidyl group.
2. The epoxy resin composition according to claim 1, wherein the aralkyl group is a structural site represented by the following structural formula (1),
in the formula (1), R1Each independently represents any of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, Ar1Is any of phenyl, naphthyl, or a structural site having 1 or more halogen atoms and an alkyl group having 1 to 4 carbon atoms on the aromatic nucleus thereof.
3. The epoxy resin composition according to claim 1, wherein a mass ratio [ (A)/(B) ] of the novolak-type epoxy resin (A) to the diphenol-type epoxy resin (B) is in a range of 99/1 to 70/30.
4. A curable composition comprising the epoxy resin composition according to any one of claims 1 to 3 and a curing agent.
5. A cured product of the curable composition according to claim 4.
6. A printed circuit board comprising the curable composition according to claim 4.
7. A semiconductor sealing material comprising the epoxy resin composition according to any one of claims 1 to 3, a curing agent, and an inorganic filler.
8. A process for producing the epoxy resin composition according to claim 1, wherein the epoxy resin composition comprises a novolak type epoxy resin (A) having an aralkyl group in a part or all of aromatic rings constituting a novolak structure and a biphenol type epoxy resin (B) which is a polyglycidyl ether of 4, 4' -biphenol,
in the above production method, a compound (x) containing a phenolic hydroxyl group as a raw material of the novolak type epoxy resin (a) and a diphenol as a raw material of the diphenol type epoxy resin (B) are mixed and then subjected to polyglycidyl etherification.
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| PCT/JP2017/010630 WO2017175560A1 (en) | 2016-04-04 | 2017-03-16 | Epoxy resin composition, curable composition, and semiconductor-encapsulating material |
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