WO2022097598A1 - ベンゾオキサジン化合物含有組成物、硬化性樹脂組成物及びその硬化物 - Google Patents
ベンゾオキサジン化合物含有組成物、硬化性樹脂組成物及びその硬化物 Download PDFInfo
- Publication number
- WO2022097598A1 WO2022097598A1 PCT/JP2021/040192 JP2021040192W WO2022097598A1 WO 2022097598 A1 WO2022097598 A1 WO 2022097598A1 JP 2021040192 W JP2021040192 W JP 2021040192W WO 2022097598 A1 WO2022097598 A1 WO 2022097598A1
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- WO
- WIPO (PCT)
- Prior art keywords
- compound
- group
- benzoxazine compound
- area
- peak area
- Prior art date
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Classifications
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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
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
-
- 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
- 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
- C08G14/02—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the present invention relates to a benzoxazine compound-containing composition, a curable resin composition, and a cured product thereof. More specifically, the present invention relates to a benzoxazine compound-containing composition having a low melt viscosity, a curable resin composition containing the benzoxazine compound-containing composition having a low melt viscosity, and a cured product thereof.
- the benzoxazine compound is known as a thermosetting resin raw material in which the benzoxazine ring is ring-opened and polymerized without producing volatile by-products by heating, and can be used as a material for an insulating substrate. It is used as a raw material for a body (Patent Document 1), a liquid crystal alignment agent (Patent Document 2), a resin composition for semiconductor encapsulation (Patent Documents 3 and 4), and the like.
- the resin composition containing the benzoxazine compound represented by the following general formula (1) in the present invention is known to improve the heat resistance (glass transition temperature: Tg) of the cured product (Patent Document 5). ) Therefore, its use as a sealing resin for semiconductors is being studied.
- the benzoxazine compound represented by the following general formula (1) in the present invention according to the production method described in Patent Documents 5 and 6 below has a high melt viscosity and is handled at a high temperature in order to reduce the melt viscosity. Since the polymerization proceeds when the attempt is made, there is a problem that the range of application to transfer molding and compression molding, which are typical semiconductor encapsulation methods, is limited.
- An object of the present invention is to provide a benzoxazine compound-containing composition represented by the following general formula (1) having a low melt viscosity, a curable resin composition using the same, and a cured product thereof.
- the present inventor has set the content of the compound group having a specific molecular weight within a specific range to obtain a benzoxazine compound-containing composition having a low melt viscosity. We found that we could obtain it and completed the present invention.
- the present invention is as follows. 1.
- It contains a benzoxazine compound represented by the following general formula (1) and a compound group (A) having a molecular weight in the range of 1,000 to 10,000.
- the peak area of the compound group (A) is 0.1 area% to 15 area% with respect to the peak area of all the detected components. It ’s a range, A benzoxazine compound-containing composition, wherein the melt viscosity at 100 ° C. is in the range of 0.1 Pa ⁇ S to 4.5 Pa ⁇ S. (In the formula, R is a hydrogen atom or a methyl group independently.) 2.
- the peak area of the benzoxazine compound represented by the general formula (1) is in the range of 62 area% to 90 area% with respect to the peak area of all the detected components. (However, the sum of the peak area of the benzoxazine compound represented by the general formula (1), the peak area of the compound group (A) and the peak area of other detected components is 100 area%), 1. ..
- Oxazine compound-containing compositions are provided.
- the benzoxazine compound-containing composition of the present invention contains the benzoxazine compound represented by the above general formula (1), which improves the heat resistance of the cured product, and has a low melt viscosity at a temperature at which polymerization does not proceed. It has excellent workability, it is possible to increase the addition rate of fillers, etc.
- the composition containing a benzoxazine compound having a low melt viscosity, the curable resin composition containing the composition, and the cured product thereof are varnishes that can be applied to various substrates, prepregs impregnated with varnishes, and prints. It can be suitably used as a resin raw material for circuit boards, encapsulants for electronic parts, electric / electronic molded parts, automobile parts, laminated materials, paints, resist inks and the like.
- the benzoxazine compound-containing composition of the present invention contains a benzoxazine compound represented by the following general formula (1).
- R is a hydrogen atom or a methyl group independently.
- Specific examples of the benzoxazine compound represented by the general formula (1) include the compound (1a), the compound (1b), and the compound (1c) exemplified by the following chemical structures.
- the benzoxazine compound represented by the general formula (1) in the present invention is selected from 3,4'-diaminodiphenyl ether and phenol, p-cresol, o-cresol, m-cresol as shown in the following reaction formula. It can be produced by a method of dehydration condensation reaction with one or more kinds of phenol compounds and formaldehyde selected from formaldehyde aqueous solution, 1,3,5-trioxane, paraformaldehyde and the like to cyclize the compound.
- R is a hydrogen atom or a methyl group independently.
- the benzoxazine compound-containing composition represented by the general formula (1) having a low melt viscosity in the present invention contains 3,4'-diaminodiphenyl ether in the presence of formaldehyde, a phenol compound and a solvent, usually for 1 to 10 hours. It can be obtained by mixing, preferably over 4 to 10 hours, more preferably over 5 to 10 hours. 3,4'-Diaminodiphenyl ether is usually mixed as a solution of phenolic compounds and / or solvents. By adding 3,4'-diaminodiphenyl ether to the reaction system over time, the content of the compound group (A) having a molecular weight in the range of 1,000 to 10,000 is within a specific range. It becomes possible to.
- the amount of the phenol compound used in the above reaction is in the range of 2.0 to 10.0 mol and in the range of 2.0 to 8.0 mol with respect to 1 mol of 3,4'-diaminodiphenyl ether. It is preferably in the range of 2.0 to 6.0 mol, more preferably.
- the amount of formaldehyde used in the above reaction is in the range of 4.0 to 20.0 mol and preferably in the range of 4.0 to 16.0 mol with respect to 1 mol of 3,4'-diaminodiphenyl ether. More preferably, it is in the range of 4.0 to 12.0 mol.
- the reaction is usually carried out in the presence of a solvent.
- the solvent is not particularly limited as long as it does not inhibit the reaction, but toluene, xylene, ethyl acetate, butyl acetate, chloroform, dichloromethane, tetrahydrofuran, dioxane and the like are preferable. These solvents can be used alone or in combination.
- the amount of the solvent used is not particularly limited as long as it does not interfere with the reaction, but is usually used in the range of 3 to 10 times by weight, preferably 4 to 6 times by weight with respect to 3,4'-diaminodiphenyl ether.
- the reaction temperature is usually in the range of 70 to 100 ° C, preferably in the range of 75 to 90 ° C.
- the reaction pressure may be carried out under normal pressure conditions, under pressure or under reduced pressure.
- a catalyst for accelerating the reaction is not particularly required, but an acid catalyst or a base catalyst can be used as needed.
- the acid catalyst that can be used include concentrated hydrochloric acid, hydrochloric acid gas, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, benzoic acid and mixtures thereof
- examples of the base catalyst that can be used include sodium hydroxide. , Sodium carbonate, triethylamine, triethanolamine and mixtures thereof, and the like, but are not limited thereto.
- a procedure for removing water derived from the raw material or water generated during the reaction to the outside of the system can be included.
- the procedure for removing the water produced from the reaction solution is not particularly limited, and the water can be distilled azeotropically with the solvent system in the reaction solution.
- the generated water can be removed from the reaction system by using, for example, an isobaric dropping funnel equipped with a cock, a Dimroth condenser, a Dean-Stark apparatus, or the like.
- the benzoxazine compound-containing composition of the present invention can be obtained from this mixture by a known method.
- an aqueous solution containing a basic compound such as a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, sodium carbonate, or potassium carbonate is added to the reaction completion solution, and the mixture is stirred (neutralized step) and allowed to stand to form an aqueous layer.
- a basic compound such as a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, sodium carbonate, or potassium carbonate
- water is added to the organic solvent layer, and the operation of stirring, standing, and separating and removing the aqueous layer (washing step) is performed multiple times to thoroughly wash the organic solvent layer, and then wash with water.
- the obtained organic solvent layer can be distilled (distilled step) to remove the solvent and the phenol compound to obtain the benzoxazine compound-containing composition of the present invention.
- the neutralization step, the washing step, and the distillation step are preferably performed in the temperature range of 0 to 50 ° C, 0 to 90 ° C, and 50 to 100 ° C, respectively.
- the benzoxazine compound-containing composition of the present invention is characterized in that the melt viscosity at 100 ° C. is in the range of 0.1 Pa ⁇ S to 4.5 Pa ⁇ S.
- the melt viscosity in the present invention means a value measured by measuring 15 g of a benzoxazine compound-containing composition using a B-type viscometer under the following measurement conditions.
- the benzoxazine compound-containing composition of the present invention preferably has a melt viscosity at 100 ° C. in the range of 0.5 Pa ⁇ S to 4.0 Pa ⁇ S, preferably in the range of 0.5 Pa ⁇ S to 3.5 Pa ⁇ S. It is more preferable to have.
- the benzoxazine compound according to the present invention When the benzoxazine compound according to the present invention is heated at a temperature exceeding 100 ° C., the decrease due to the progress of the polymerization of the benzoxazine compound and the increase of the high molecular weight components such as the compound group (A) rapidly progress.
- the benzoxazine compound-containing composition of the present invention is very useful because it has a low melt viscosity at a temperature at which such polymerization does not proceed.
- the benzoxazine compound-containing composition of the present invention has a peak area of the compound group (A) having a molecular weight in the range of 1,000 to 10,000 in the measurement of gel permeation chromatography using a differential refractive index as a detector. It is characterized in that it is contained in the range of 0.1 area% to 15 area% with respect to the peak area of all the detected components.
- the compound group (A) is a benzoxazine compound represented by the above general formula (1) and the compound group (A) is expanded and contracted by benzene ring CH at 2850 cm -1 .
- the compound group (A) is characterized in that the peak intensity near 3000 cm -1 is weak when the peak intensities are compared by standardizing the peaks in the vicinity.
- the peak area of this compound group (A) is preferably in the range of 0.1 area% to 14 area% with respect to the peak area of all the detected components, and is preferably 0.1 area% to 13 area%. It is more preferably in the range of 0.1 area% to 12 area%.
- the peak area of the benzoxazine compound represented by the above general formula (1) becomes the peak area of all the detected components.
- the peak area of the benzoxazine compound represented by the general formula (1) is 100 area%.
- the peak area of the benzoxazine compound represented by the general formula (1) is more preferably contained in the range of 64 area% to 90 area% with respect to the peak area of all the detected components, 65. It is more preferably contained in the range of area% to 90 area%.
- the measurement of gel permeation chromatography using the differential refractometer of the benzoxazine compound-containing composition of the present invention as a detector means a numerical value measured under the following measurement conditions.
- Measurement condition Flow rate: 1 mL / min
- Eluent Tetrahydrofuran Temperature: 40 ° C
- Wavelength 254 nm
- Sampling pitch 100 msec
- Measurement sample A solution of 10 mg of a benzoxazine compound-containing composition diluted 600-fold with tetrahydrofuran Injection amount: 20 ⁇ L
- the benzoxazine compound-containing composition represented by the general formula (1) obtained by a conventionally known method or the above-mentioned method can be obtained.
- Produced by mixing the obtained benzoxazine compound-containing composition and crystals of the benzoxazine compound represented by the general formula (1) obtained by the following method so as to be the benzoxazine compound-containing composition of the present invention. can do.
- this mixing method there are a method of mixing each of them in a solid state and melting them to obtain a uniform composition, and a method of mixing each of them in a melted state to obtain a uniform composition.
- the method for obtaining the crystal of the benzoxazine compound represented by the general formula (1) is obtained by reacting 3,4'-diaminodiphenyl ether with the 2-hydroxybenzaldehyde compound (3) as shown in the following reaction formula.
- the compound represented by the general formula (2) is reduced with sodium hydride or the like to form a compound represented by the general formula (4), and then reacted with formalin to be represented by the general formula (1).
- This is a method for obtaining a benzoxazine compound.
- the benzoxazine compound represented by the general formula (1) obtained by this method can be obtained as high-purity crystals.
- R is a hydrogen atom or a methyl group independently.
- the benzoxazine compound-containing composition of the present invention can be used as a curable resin composition containing this as an essential component.
- One embodiment thereof includes the benzoxazine compound-containing composition of the present invention, silicon oxide, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, silicon nitride, silicon carbide, an inorganic filler such as hexagonal boron nitride, and carbon.
- reinforcing fibers such as fibers, glass fibers, organic fibers, boron fibers, steel fibers, and aramid fibers are mixed.
- a curable resin composition containing the benzoxazine compound-containing composition of the present invention as an essential component and containing other polymer materials.
- the polymer material constituting the curable resin composition of the present invention is not particularly limited, but is an epoxy resin, a phenol resin, a bismaleimide resin, and a benzoxazine compound other than the benzoxazine compound represented by the general formula (1).
- Each raw material can be contained.
- this epoxy resin include orthocresol type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin, anthracendihydride type epoxy resin, brominated novolak type epoxy resin and the like.
- the phenol resin include a novolak type phenol resin and a bisphenol resin
- examples of the bismaleimide resin include raw materials for a bismaleimide resin having the following structure.
- benzoxazine compound other than the benzoxazine compound represented by the general formula (1) examples include benzoxazine compounds having structures represented by the following general formulas (A) to (C).
- Ra represents a divalent group having 1 to 30 carbon atoms (excluding diphenyl ether-3,4'-diyl), and Rb has 1 carbon atom which may independently have a substituent. It represents a monovalent group of -10, where n represents 0 or 1).
- Rc represents a divalent group having 1 to 30 carbon atoms, a direct bond, an oxygen atom, a sulfur atom, a carbonyl group, or a sulfonyl group
- Rd is 1 of 1 to 10 carbon atoms independently. Indicates the basis of valence.
- Re independently indicates a monovalent group having 1 to 10 carbon atoms, and m indicates 0 or 1.
- Ra in the benzoxazine compound having the structure represented by the general formula (A) represents a divalent group having 1 to 30 carbon atoms excluding diphenyl ether-3,4'-diyl. Specific examples thereof include alkylene groups such as 1,2-ethylene, 1,4-butylene and 1,6-hexylene, and alkylenes containing cyclic structures such as 1,4-cyclohexylene, dicyclopentadienylene and adamantylene.
- Rb in the benzoxazine compound having a structure represented by the general formula (A) independently represents a monovalent group having 1 to 10 carbon atoms.
- alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an alkenyl group such as a vinyl group and an allyl group, an alkynyl group such as an ethynyl group and a propargyl group, and an aryl such as a phenyl group and a naphthyl group.
- alkoxy group having 1 to 4 carbon atoms an acyl group having 1 to 4 carbon atoms, a halogen atom, a carboxyl group, a sulfo group, an allyloxy group, a hydroxy group and a thiol group.
- benzoxazine compound having the structure represented by the general formula (A) include P-d type benzoxazine manufactured by Shikoku Kasei, JBZ-OP100N and JBZ-BP100N manufactured by JFE Chemical.
- Rc in the benzoxazine compound having a structure represented by the general formula (B) represents a divalent group having 1 to 30 carbon atoms, a direct bond, an oxygen atom, a sulfur atom, a carbonyl group, or a sulfonyl group.
- Divalent groups having 1 to 30 carbon atoms include alkylene groups such as methylene, 1,2-ethylene, 1,4-butylene and 1,6-hexylene, 1,4-cyclohexylene and dicyclopentadienylene.
- Alkylene group containing cyclic structure such as adamantylene, ethylidene, propyridene, isopropyridene, butylidene, phenylethylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclododecylidene, 3,3,5-trimethylcyclohexy Examples thereof include an alkylidene group such as silidene and fluorenylidene.
- Rd in the benzoxazine compound having the structure represented by the general formula (B) independently represents a monovalent group having 1 to 10 carbon atoms.
- alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an alkenyl group such as a vinyl group and an allyl group, an alkynyl group such as an ethynyl group and a propargyl group, and an aryl such as a phenyl group and a naphthyl group.
- substituents include an alkoxy group having 1 to 4 carbon atoms, an acyl group having 1 to 4 carbon atoms, a halogen atom, a carboxyl group, a sulfo group, an allyloxy group, a hydroxy group and a thiol group.
- benzoxazine compound having a structure represented by the general formula (B) examples include FA-type benzoxazine manufactured by Shikoku Kasei and BS-BXZ manufactured by Konishi Chemical Industry.
- Re in the benzoxazine compound having the structure represented by the general formula (C) independently represents a monovalent group having 1 to 10 carbon atoms.
- Specific examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an alkenyl group such as a vinyl group and an allyl group, an alkynyl group such as an ethynyl group and a propargyl group, and an aryl such as a phenyl group and a naphthyl group.
- the curable resin composition of the present invention includes a benzoxazine compound-containing composition represented by the above general formula (1), an epoxy resin, and a benzoxazine compound other than the benzoxazine compound represented by the general formula (1). It is preferable to contain at least one selected from the group consisting of the novolak type phenol resin and the novolak type phenol resin.
- the mixing amount of the benzoxazine compound-containing composition represented by the above general formula (1) and other polymer materials in the curable resin composition of the present invention is the benzoxazine compound represented by the above general formula (1). It is in the range of 0.01 parts by weight to 100 parts by weight with respect to 1 part by weight of the contained composition.
- the curable resin composition of the present invention can be obtained by adding a benzoxazine compound-containing composition represented by the above general formula (1) to the polymer material as needed, and the method of addition is such a method.
- the method is not particularly limited, and a conventionally known method can be adopted.
- a method of adding a polymer material during synthesis or polymerization a method of adding a resin made of a polymer material to a molten resin melted in, for example, a melt extrusion step, a method of impregnating a resin product made of a polymer material, etc.
- a resin made of a polymer material to a molten resin melted in, for example, a melt extrusion step
- a method of impregnating a resin product made of a polymer material etc.
- the temperature of this vacuum degassing treatment is not particularly limited as long as it is a temperature at which the resin composition of the present invention is in a molten state, but the upper limit is 140 ° C. because curing does not proceed and degassing is easy. It is preferable to carry out as.
- the pressure of the vacuum degassing treatment is not particularly limited, but it is better to be low (high degree of decompression), and it may be performed in air or in a nitrogen substitution atmosphere. This vacuum degassing process is performed until bubbles cannot be visually confirmed.
- the curable resin composition of the present invention includes silicon oxide, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, silicon nitride, silicon carbide, and inorganic fillers such as hexagonal boron nitride, depending on the needs of the application. It can be used by mixing with reinforcing fibers such as carbon fiber, glass fiber, organic fiber, boron fiber, steel fiber and aramid fiber.
- the cured product of the present invention can be obtained by curing the benzoxazine compound-containing composition represented by the general formula (1) of the present invention or the curable resin composition of the present invention.
- a method for producing a cured product of the present invention for example, a method of heating to a predetermined temperature to cure, a method of heating and melting and pouring into a mold or the like to further heat the mold to cure and mold, and a method of preheating the melt. Examples thereof include a method of injecting into a mold and hardening the mold.
- the cured product of the present invention can be cured by ring-opening polymerization under the same curing conditions as ordinary benzoxazine.
- the curing temperature is usually in the temperature range of 140 to 250 ° C., preferably in the temperature range of 160 to 220 ° C., more preferably in the temperature range of 160 to 200 ° C., but the mechanical properties of the obtained cured product are good.
- the temperature range is preferably 180 to 200 ° C.
- the reaction time may be about 2 to 10 hours.
- the resin composition of the present invention can be cured only by heat, but it is preferable to use a curing accelerator depending on the components other than the benzoxazine compound represented by the above general formula (1) and the content thereof.
- the curing accelerator that can be used is not particularly limited, and is, for example, 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, tris (2,4,6-dimethylaminomethyl).
- Tertiary amines such as phenol, imidazoles such as 2-ethyl-4-methylimidazole and 2-methylimidazole, triphenylphosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, tetra-n-butylphosphonium Examples thereof include phosphorus compounds such as - ⁇ , ⁇ -diethylphosphologithioate, quaternary ammonium salts, organic metal salts, and derivatives thereof. These may be used alone or in combination.
- tertiary amines imidazoles and phosphorus compounds.
- TSKgel Standard Polystyrene A-500 Nominal Mol. Wt. 5.9 x 102 Mw / Mn 1.19 (0005203 / manufactured by Tosoh Corporation)
- TSKgel Standard Polystyrene A-2500 Nominal Mol. Wt. 2.63 x 103 Mw / Mn 1.05 (0005205 / manufactured by Tosoh Corporation)
- TSKgel Standard Polystyrene A-5000 Nominal Mol. Wt.
- TSKgel Standard Polystyrene F-1 Nominal Mol. Wt. 1.02 x 104 Mw / Mn 1.02 (0005207 / manufactured by Tosoh Corporation)
- TSKgel Standard Polystyrene F-2 Nominal Mol. Wt. 1.74 ⁇ 104 Mw / Mn 1.01 (0005208 / manufactured by Tosoh Corporation)
- TSKgel Standard Polystyrene F-4 Nominal Mol. Wt. 3.79 ⁇ 104 Mw / Mn 1.01 (0005209 / manufactured by Tosoh Corporation)
- Example 1 92 wt% paraformaldehyde 547 g (16.8 mol), toluene 3336 g, and phenol 394 g (4.19 mol) were charged in a four-necked flask equipped with a thermometer, agitator, and a cooling tube, and the reaction vessel was replaced with nitrogen.
- melt viscosity of the obtained 15 g of the compound (1a) -containing composition measured at 100 ° C. using a B-type viscometer (TVB-10 / manufactured by Toki Sangyo Co., Ltd.) under the above measurement conditions is It was 1.8 Pa ⁇ S.
- Example 2 After undergoing the preparation, reaction, and liquid separation steps in the same manner as in Example 1, the final temperature of the distillation step was set to 95 ° C. The melt of the composition containing the compound (1a) was withdrawn, cooled and solidified, and then pulverized to obtain 1280 g of the composition containing the compound (1a). As a result of gel permeation chromatography analysis of the obtained composition containing compound (1a) using a differential refractometer as a detector, the peak area ratio of compound (1a) was 69.0 area%, and the compound group. The peak area ratio of (A) was 11.3 area%. The chart of this gel permeation chromatography analysis is shown in FIG. The melt viscosity at 100 ° C. was 2.7 Pa ⁇ S.
- Example 3 The same procedure as in Example 1 was carried out except that the solution was intermittently added dropwise over 4.5 hours to obtain the compound (1a) -containing composition.
- the peak area ratio of compound (1a) was 69.4 area%, and the compound group.
- the peak area ratio of (A) was 9.4 area%.
- the chart of this gel permeation chromatography analysis is shown in FIG.
- the melt viscosity at 100 ° C. was 2.0 Pa ⁇ S.
- Example 4 The same procedure as in Example 1 was carried out except that 3,4'-diaminodiphenyl ether, phenol and paraformaldehyde were charged in a molar ratio of 1: 4: 8 to obtain the above compound (1a) -containing composition.
- the peak area ratio of compound (1a) was 72.8 area%, and the compound group.
- the peak area ratio of (A) was 8.0 area%.
- the chart of this gel permeation chromatography analysis is shown in FIG. The melt viscosity at 100 ° C. was 1.5 Pa ⁇ S.
- Example 5 The same procedure as in Example 1 was carried out except that the solution was intermittently added dropwise over 1 hour to obtain the compound (1a) -containing composition.
- the peak area ratio of compound (1a) was 65.4 area%, and the compound group.
- the peak area ratio of (A) was 14.9 area%.
- the chart of this gel permeation chromatography analysis is shown in FIG.
- the melt viscosity at 100 ° C. was 2.2 Pa ⁇ S.
- Example 6 The same procedure as in Example 1 was carried out except that the solution was intermittently added dropwise over 2 hours to obtain the compound (1a) -containing composition.
- the peak area ratio of compound (1a) was 68.3 area%, and the compound group.
- the peak area ratio of (A) was 11.6 area%.
- the chart of this gel permeation chromatography analysis is shown in FIG.
- the melt viscosity at 100 ° C. was 2.0 Pa ⁇ S.
- Example 7 The same procedure as in Example 1 was carried out except that the reaction-generated water was removed by reducing the pressure in the reaction step after intermittent dropping to obtain the above compound (1a) -containing composition.
- the peak area ratio of compound (1a) was 62.7 area%, and the compound group.
- the peak area ratio of (A) was 11.8 area%.
- the chart of this gel permeation chromatography analysis is shown in FIG.
- the melt viscosity at 100 ° C. was 2.1 Pa ⁇ S.
- Example 3 The same procedure as in Example 1 was carried out except that the solution was added all at once to obtain the compound (1a) -containing composition.
- the peak area ratio of compound (1a) was 49.5 area%, and the compound group.
- the peak area ratio of (A) was 29.8 area%.
- the chart of this gel permeation chromatography analysis is shown in FIG.
- the melt viscosity at 100 ° C. was 19.1 Pa ⁇ S.
- the reaction solution containing the compound represented by the above formula (2a) was cooled to 25 ° C., 1138 g of ethanol was added, and 53 g (1.39 mol) of sodium borohydride was intermittently added over 2 hours. Then, the mixture was stirred at 25 ° C. for 7 hours. After completion of the reaction, 1510 g of water was added, and the mixture was stirred at 25 ° C. for 14 hours. The obtained slurry liquid was separated into solid and liquid by filtration to obtain a solid substance. The obtained solid was washed twice with 300 g of a 30% aqueous methanol solution with 500 g of water, and then dried under reduced pressure at 50 ° C.
- Example 8 The compound (1a) -containing composition obtained in the same manner as in Example 3 and the compound (1a) -containing composition obtained in Comparative Example 4 were melt-mixed to obtain a compound (1a) -containing composition.
- the peak area ratio of compound (1a) was 79.7 area%, and the compound group.
- the peak area ratio of (A) was 7.8 area%.
- the chart of this gel permeation chromatography analysis is shown in FIG.
- the melt viscosity at 100 ° C. was 1.4 Pa ⁇ S.
- Example 9 The compound (1a) -containing composition obtained by the same method as in Example 3 and the compound (1a) -containing composition obtained in Comparative Example 4 are melt-mixed at a weight ratio different from that of Example 8 to obtain the compound (1a). The contained composition was obtained.
- the peak area ratio of compound (1a) was 87.7 area%, and the compound group.
- the peak area ratio of (A) was 4.9 area%.
- the chart of this gel permeation chromatography analysis is shown in FIG.
- the melt viscosity at 100 ° C. was 1.1 Pa ⁇ S.
- the benzoxazine compound-containing compositions of Comparative Examples 1 to 3, which are not specific examples of the present invention, have a high melt viscosity, and the range of application to, for example, transfer molding and compression molding, which are typical semiconductor encapsulation methods, is limited. It became clear that it would end up. Further, it was clarified that the benzoxazine compound-containing composition of Comparative Example 4, which is not a specific example of the present invention, does not melt at 100 ° C., further limiting the range of application to various molding methods.
- the peak area ratio of the compound group (A) is within a specific range, so that the composition has a temperature of 100 ° C. It was revealed that the melt viscosity in was significantly reduced.
- the benzoxazine compound represented by the general formula (1) which improves heat resistance, has excellent workability, and the addition rate of fillers and the like can be increased, which greatly contributes to the improvement of heat dissipation. Since it is possible to enclose a semiconductor having a precise structure, it can be used in a wide range of applications, and it has been clarified that it is very useful.
- TSKgel Standard Polystyrene A-500 Nominal Mol. Wt. 5.9 ⁇ 10 2 Mw / Mn 1.19 (0005203 / manufactured by Tosoh Corporation)
- TSKgel Standard Polystyrene A-2500 Nominal Mol. Wt. 2.63 ⁇ 10 3 Mw / Mn 1.05 (0005205 / manufactured by Tosoh Corporation)
- TSKgel Standard Polystyrene A-5000 Nominal Mol. Wt. 5.06 ⁇ 10 3 Mw / Mn 1.02 (0005206 / manufactured by Tosoh Corporation)
- TSKgel Standard Polystyrene F-1 Nominal Mol. Wt.
- TSKgel Standard Polystyrene F-2 Nominal Mol. Wt. 1.74 ⁇ 10 4 Mw / Mn 1.01 (0005208 / manufactured by Tosoh Corporation)
- TSKgel Standard Polystyrene F-4 Nominal Mol. Wt. 3.79 ⁇ 10 4 Mw / Mn 1.01 (0005209 / manufactured by Tosoh Corporation)
- ⁇ GPC-FTIR analysis result> The chromatogram and peak position obtained by the RI detector are shown in FIG. Peak 7 in FIG. 14 is the peak of compound (1a). Since the injection amount was increased for the purpose of increasing the IR sensitivity, the separation of peak 4 and peak 6 was insufficient.
- the average molecular weight of each peak is shown in Table 1 below. In Table 1, "Mn” means a number average molecular weight, “Mw” means a weight average molecular weight, “Mz” means an average molecular weight, and "Mw / Mn” means a polydispersity.
- the peak 1 in FIG. 14 is the peak of the compound group (A) having a molecular weight in the range of 1,000 to 10,000 in the present invention.
- FT at the peak tops of peak 1 (peak showing compound group (A) having a molecular weight in the range of 1,000 to 10,000 in the present invention) and peak 7 (peak showing compound (1a)) in FIG. -IR spectra are shown in FIGS. 15 and 16.
- the FT-IR spectra in the range of 2600 to 3200 cm -1 are shown in FIG. 17 when normalized by the peak of 2849 cm -1 which is the expansion and contraction of the benzene ring CH.
- the compound group (A) (peak 1) having a molecular weight in the range of 1,000 to 10,000 of the present invention is characterized in that the peak intensity near 3000 cm -1 is weaker than that of the compounds (1a) (peak 7). It became clear that there was.
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Abstract
Description
本発明における下記一般式(1)で表されるベンゾオキサジン化合物を含有する樹脂組成物は、その硬化物の耐熱性(ガラス転移温度:Tg)を向上させることが知られている(特許文献5)ことから、半導体の封止樹脂としての用途が検討されている。
しかしながら、下記特許文献5、6等に記載された製造方法による、本発明における下記一般式(1)で表されるベンゾオキサジン化合物は溶融粘度が高く、溶融粘度を下げるために高い温度で取り扱おうとすると重合が進行してしまうため、代表的な半導体封止方法であるトランスファー成形や、コンプレッション成形への適用範囲が限定されるという問題があった。
1.下記一般式(1)で表されるベンゾオキサジン化合物と、分子量が1,000~10,000の範囲にある化合物群(A)を含有し、
示差屈折計を検出器とするゲル浸透クロマトグラフィーの測定において、前記化合物群(A)のピーク面積が、検出される全ての成分のピーク面積に対して、0.1面積%~15面積%の範囲であって、
100℃における溶融粘度が0.1Pa・S~4.5Pa・Sの範囲にあることを特徴とする、ベンゾオキサジン化合物含有組成物。
2.前記ゲル浸透クロマトグラフィーの測定において、前記一般式(1)で表されるベンゾオキサジン化合物のピーク面積が、検出される全ての成分のピーク面積に対して62面積%~90面積%の範囲である(ただし、前記一般式(1)で表されるベンゾオキサジン化合物のピーク面積、前記化合物群(A)のピーク面積及びその他の検出される成分のピーク面積の総和は100面積%である)、1.に記載のベンゾオキサジン化合物含有組成物。
3.1.又は2.に記載のベンゾオキサジン化合物含有組成物を含む硬化性樹脂組成物。
4.1.又は2.に記載のベンゾオキサジン化合物含有組成物と、エポキシ樹脂、前記一般式(1)で表されるベンゾオキサジン化合物以外のベンゾオキサジン化合物及びノボラック型フェノール樹脂からなる群より選択される1種以上を含有する、3.に記載の硬化性樹脂組成物。
5.3.又は4.に記載の硬化性樹脂組成物を硬化させてなる硬化物。
本発明のベンゾオキサジン化合物含有組成物は、その硬化物の耐熱性を向上させる上記一般式(1)で表されるベンゾオキサジン化合物を含有し、かつ、重合が進行しない温度における溶融粘度が低いため、作業性に優れること、硬化性樹脂組成物とした際にフィラー等の添加率を上げることが可能となり、放熱性向上に大きく寄与すること、より精密な構造を有する半導体の封止が可能となることなど、幅広い用途で利用できるようになるため、非常に有用である。
本発明における、低溶融粘度のベンゾオキサジン化合物含有組成物や、当該組成物を含有する硬化性樹脂組成物とその硬化物は、各種基材に塗布可能なワニス、ワニスを含浸させたプリプレグ、プリント回路基板、電子部品の封止剤、電気・電子成型部品、自動車部品、積層材、塗料、レジストインク等の樹脂原料として好適に用いることができる。
前記一般式(1)で表されるベンゾオキサジン化合物として、具体的には、下記の化学構造で例示する化合物(1a)、化合物(1b)、化合物(1c)が挙げられる。
上記反応におけるフェノール化合物の使用量は、3,4’-ジアミノジフェニルエーテル1モルに対して、2.0~10.0モルの範囲であり、2.0~8.0モルの範囲であることが好ましく、2.0~6.0モルの範囲であることがより好ましい。
上記反応におけるホルムアルデヒド類の使用量は、3,4’-ジアミノジフェニルエーテル1モルに対して4.0~20.0モルの範囲であり、4.0~16.0モルの範囲であることが好ましく、4.0~12.0モルの範囲であることがより好ましい。
反応温度は通常、70~100℃の範囲であり、好ましくは75~90℃の範囲である。反応圧力は常圧条件下で行ってもよく、また、加圧下でも、或は減圧下で行ってもよい。
反応を促進するための触媒は特に必要はないが、必要に応じて、酸触媒または塩基触媒を使用することができる。この場合、使用できる酸触媒として、濃塩酸、塩酸ガス、トリフルオロ酢酸、メタンスルホン酸、p-トルエンスルホン酸、安息香酸及びそれらの混合物等が挙げられ、使用できる塩基触媒としては、水酸化ナトリウム、炭酸ナトリウム、トリエチルアミン、トリエタノールアミン及びそれらの混合物等が挙げられるが、これらに限定されるものではない。
別の態様として、原料に由来する水若しくは反応中に生成した水を系外に除去する手順を含むことができる。反応溶液から生成した水を除去する手順は特に制限されず、生成した水を反応溶液中の溶媒系と共沸的に蒸留することにより行うことができる。生成した水は、例えばコックを備えた等圧滴下漏斗、ジムロート冷却器、ディーンスターク装置等の使用により反応系外に除去することができる。
本発明における溶融粘度は、ベンゾオキサジン化合物含有組成物15gを、B型粘度計を使用して、下記測定条件で測定した数値を意味する。
[測定条件]
溶融液温度:100℃
測定時間:組成物完溶後15分以内
完溶までに要する時間:オイルバス温100℃(±5℃)で1時間程度
回転数:6.0rpm
本発明のベンゾオキサジン化合物含有組成物は、100℃における溶融粘度が0.5Pa・S~4.0Pa・Sの範囲にあることが好ましく、0.5Pa・S~3.5Pa・Sの範囲にあることがより好ましい。
本発明にかかるベンゾオキサジン化合物は、100℃を超える温度で加熱をすると、ベンゾオキサジン化合物の重合の進行による減少と、化合物群(A)等の高分子量の成分の増加が急速に進んでしまう。しかしながら、本発明のベンゾオキサジン化合物含有組成物は、このような重合が進行しない温度における溶融粘度が低いため非常に有用である。
化合物群(A)は、赤外分光法(IR)による分析において、上記一般式(1)で表されるベンゾオキサジン化合物と化合物群(A)を、ベンゼン環C-H伸縮である2850cm-1付近のピークで規格化してピーク強度を比較したときに、化合物群(A)は3000cm-1付近のピーク強度が弱いことを特徴とする。
この化合物群(A)のピーク面積は、検出される全ての成分のピーク面積に対して、0.1面積%~14面積%の範囲であることが好ましく、0.1面積%~13面積%の範囲であることがより好ましく、0.1面積%~12面積%であることが特に好ましい。
また、本発明のベンゾオキサジン化合物含有組成物は、前記ゲル浸透クロマトグラフィーの測定において、上記一般式(1)で表されるベンゾオキサジン化合物のピーク面積が、検出される全ての成分のピーク面積に対して62面積%~82面積%の範囲で含有している場合でもあってもよいが、検出される全ての成分のピーク面積に対して62面積%~90面積%の範囲で含有していることが好適である。ただし、一般式(1)で表されるベンゾオキサジン化合物のピーク面積、化合物群(A)のピーク面積及びその他の検出される成分のピーク面積の総和は100面積%である。この一般式(1)で表されるベンゾオキサジン化合物のピーク面積は、検出される全ての成分のピーク面積に対して64面積%~90面積%の範囲で含有していることがより好ましく、65面積%~90面積%の範囲で含有していることがさらに好ましい。
[測定条件]
流量:1mL/min
溶出液:テトラヒドロフラン
温度:40℃
波長:254nm
サンプリングピッチ:100msec
測定試料:ベンゾオキサジン化合物含有組成物10mgをテトラヒドロフランで600倍に希釈した溶液
注入量:20μL
[カラム](上流から、下記のカラムもしくはそれに相当する物を使用。)
・TSKgel Guard Column HXL-L(東ソー(株)製)
・TSKgel G4000HXL(東ソー(株)製)(充填剤:スチレンジビニルベンゼンポリマー、排除限界:4×105、理論段数:16000、カタログ値)
・TSKgel G3000HXL(東ソー(株)製)(充填剤:スチレンジビニルベンゼンポリマー、排除限界:6×104、理論段数:16000、カタログ値)
・TSKgel G2000HXL(東ソー(株)製)(充填剤:スチレンジビニルベンゼンポリマー、排除限界:1×104、理論段数:16000、カタログ値) 2本
[分子量算出方法]
ポリスチレン標準試料を用いた3次近似曲線の検量線を利用した、標準ポリスチレン換算分子量として算出する。
この混合方法としては、固体状態であるそれぞれを混合して、溶融することで均一な組成物とする方法や、溶融状態であるそれぞれを混合することで均一な組成物を得る方法などがある。酸素の影響で劣化を防止するために窒素などの不活性ガス雰囲気下に行うことが好ましい。
一般式(1)で表されるベンゾオキサジン化合物の結晶を得る方法は、下記反応式に示すとおり、3,4’-ジアミノジフェニルエーテルと、2-ヒドロキシベンズアルデヒド化合物(3)とを反応させて得られた一般式(2)で表される化合物を、水素化ホウ素ナトリウム等で還元して一般式(4)で表される化合物とした後、ホルマリンと反応させて一般式(1)で表されるベンゾオキサジン化合物を得る方法である。当該方法により得られる一般式(1)で表されるベンゾオキサジン化合物は、高純度な結晶として得ることが出来る。
その一態様として、本発明のベンゾオキサジン化合物含有組成物と、酸化珪素、酸化アルミニウム、酸化マグネシウム、窒化ホウ素、窒化アルミニウム、窒化珪素、炭化珪素があり、六方晶窒化ホウ素等の無機フィラーや、炭素繊維、ガラス繊維、有機繊維、ボロン繊維、スチール繊維、アラミド繊維等の強化繊維とを混合した硬化性樹脂組成物がある。
本発明の硬化性樹脂組成物を構成する高分子材料としては、特に制限はないが、エポキシ樹脂、フェノール樹脂、ビスマレイミド樹脂、一般式(1)で表されるベンゾオキサジン化合物以外のベンゾオキサジン化合物それぞれの原料を含有することができる。
このエポキシ樹脂としては、オルソクレゾール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂、アントラセンジヒドリド型エポキシ樹脂、臭素化ノボラック型エポキシ樹脂等が挙げられる。
このフェノール樹脂としては、ノボラック型フェノール樹脂、ビスフェノール樹脂等を、このビスマレイミド樹脂としては、下記構造を有するビスマレイミド樹脂の原料等が挙げられる。
一般式(A)で表される構造を有するベンゾオキサジン化合物におけるRbは、各々独立して炭素原子数1~10の1価の基を示す。その具体例としては、メチル基、エチル基、プロピル基、ブチル基等のアルキル基、ビニル基、アリル基等のアルケニル基、エチニル基、プロパルギル基等のアルキニル基、フェニル基、ナフチル基等のアリール基等が挙げられ、これらの基には更に、炭素原子数1~4のアルコキシ基、炭素原子数1~4のアシル基、ハロゲン原子、カルボキシル基、スルホ基、アリルオキシ基、ヒドロキシ基、チオール基等の置換基を有してもよい。
一般式(A)で表される構造を有するベンゾオキサジン化合物としては、例えば、四国化成製P-d型ベンゾオキサジン、JFEケミカル製JBZ-OP100N、JBZ-BP100Nが挙げられる。
一般式(B)で表される構造を有するベンゾオキサジン化合物におけるRdは、各々独立して炭素原子数1~10の1価の基を示す。その具体例としては、メチル基、エチル基、プロピル基、ブチル基等のアルキル基、ビニル基、アリル基等のアルケニル基、エチニル基、プロパルギル基等のアルキニル基、フェニル基、ナフチル基等のアリール基が挙げられ、これらの置換基には更に、炭素原子数1~4のアルコキシ基、炭素原子数1~4のアシル基、ハロゲン原子、カルボキシル基、スルホ基、アリルオキシ基、ヒドロキシ基、チオール基等の置換基を有してもよい。
一般式(B)で表される構造を有するベンゾオキサジン化合物としては、例えば、四国化成製F-a型ベンゾオキサジン、小西化学工業製BS-BXZが挙げられる。
中でも、本発明の硬化性樹脂組成物は、上記一般式(1)で表されるベンゾオキサジン化合物含有組成物と、エポキシ樹脂、一般式(1)で表されるベンゾオキサジン化合物以外のベンゾオキサジン化合物及びノボラック型フェノール樹脂からなる群より選択される1種以上を含有することが好ましい。
本発明の硬化性樹脂組成物は、上記一般式(1)で表されるベンゾオキサジン化合物含有組成物を、その他必要に応じて前記高分子材料に添加することによって得られるが、かかる添加方法は特に限定されず、従来公知の方法を採用することができる。例えば、高分子材料の合成や重合中に添加する方法、高分子材料からなる樹脂を例えば溶融押出工程等において溶融した溶融樹脂に添加する方法、高分子材料からなる樹脂製品等に含浸する方法等を挙げることができる。
本発明の硬化性樹脂組成物は、組成物中に水や残存溶媒を含んでいると硬化時に気泡が発生してしまうので、これを防ぐために前処理として真空脱気処理を行うことが好ましい。この真空脱気処理の温度は、本発明の樹脂組成物が溶融状態となる温度であれば特に制限されないが、硬化が進行せず、かつ、脱気がしやすいとの理由により140℃を上限として行うのが好ましい。真空脱気処理の圧力は、特に制限はないが、低い(減圧度の高い)方がよく、空気中でも窒素置換雰囲気下中の何れで行ってもよい。この真空脱気処理は、気泡が目視で確認できなくなるまで行う。
本発明の硬化性樹脂組成物は、用途の必要に応じて、酸化珪素、酸化アルミニウム、酸化マグネシウム、窒化ホウ素、窒化アルミニウム、窒化珪素、炭化珪素があり、六方晶窒化ホウ素等の無機フィラーや、炭素繊維、ガラス繊維、有機繊維、ボロン繊維、スチール繊維、アラミド繊維等の強化繊維と混合して使用することができる。
本発明の硬化物は、本発明の一般式(1)で表されるベンゾオキサジン化合物含有組成物又は本発明の硬化性樹脂組成物を硬化させて得ることができる。
本発明の硬化物の製造方法としては、例えば、所定の温度まで加熱して硬化させる方法、加熱融解させて金型等に注ぎ金型を更に加熱して硬化成型させる方法、溶融物を予め加熱された金型に注入して硬化させる方法等を挙げることができる。
本発明の樹脂組成物は、熱のみで硬化できるが、上記一般式(1)で表されるベンゾオキサジン化合物以外の成分やその含有量等によっては、硬化促進剤を用いた方が好ましい。使用できる硬化促進剤としては、特に限定されるものではなく、例えば、1,8-ジアザ-ビシクロ[5.4.0]ウンデセン-7、トリエチレンジアミン、トリス(2,4,6-ジメチルアミノメチル)フェノール等の第三級アミン類、2-エチル-4-メチルイミダゾール、2-メチルイミダゾール等のイミダゾール類、トリフェニルホスフィン、テトラフェニルホスホニウムブロマイド、テトラフェニルホスホニウムテトラフェニルボレート、テトラ-n-ブチルホスホニウム-О,О-ジエチルホスホロジチオエート等のリン化合物、4級アンモニウム塩、有機金属塩類、及びこれらの誘導体等が挙げられる。これらは単独で使用してもよく、あるいは、併用してもよい。これら硬化促進剤の中では、第三級アミン類、イミダゾール類及びリン化合物を用いることが好ましい。
なお、以下の例における物性値は、次の方法により測定した。
<分析方法>
1.溶融粘度
装置:B型粘度計(TVB-10、ローター:THM-12/東機産業(株)製)
[測定条件]
サンプル量:ベンゾオキサジン化合物含有組成物15g
溶融液温度:100℃
測定時間:組成物完溶後15分以内
完溶までに要する時間:オイルバス温100℃(±5℃)で1時間程度
回転数:6.0rpm
2.ゲル浸透クロマトグラフィー
装置:HLC-8320/東ソー(株)製
検出器:示差屈折計(RI)
[測定条件]
流量:1mL/min
溶出液:テトラヒドロフラン
温度:40℃
波長:254nm
サンプリングピッチ:100msec
測定試料:ベンゾオキサジン化合物含有組成物10mgをテトラヒドロフランで600倍に希釈した溶液
注入量:20μL
[カラム](上流から)
Guard ColumnHXL-L+G4000HXL+G3000HXL+G2000HXL×2本(7.8mmID×30cm、東ソー(株)製)
[分子量算出方法]
下記のポリスチレン標準試料を用いた3次近似曲線の検量線を利用した、標準ポリスチレン換算分子量として算出した。
測定条件は、注入量のみ10μLに変更し、それ以外は上記測定条件と同様に測定した。
(ポリスチレン標準試料)
・TSKgel Standard Polystyrene A-500:Nominal Mol.Wt. 5.9×102 Mw/Mn 1.19(0005203/東ソー(株)製)
・TSKgel Standard Polystyrene A-2500:Nominal Mol.Wt. 2.63×103 Mw/Mn 1.05(0005205/東ソー(株)製)
・TSKgel Standard Polystyrene A-5000:Nominal Mol.Wt. 5.06×103 Mw/Mn 1.02(0005206/東ソー(株)製)
・TSKgel Standard Polystyrene F-1:Nominal Mol.Wt. 1.02×104 Mw/Mn 1.02(0005207/東ソー(株)製)
・TSKgel Standard Polystyrene F-2:Nominal Mol.Wt. 1.74×104 Mw/Mn 1.01(0005208/東ソー(株)製)
・TSKgel Standard Polystyrene F-4:Nominal Mol.Wt. 3.79×104 Mw/Mn 1.01(0005209/東ソー(株)製)
温度計、撹拌機、冷却管を備えた4つ口フラスコに92重量%のパラホルムアルデヒド547g(16.8mol)、トルエン3336g、フェノール394g(4.19mol)を仕込み、反応容器を窒素置換した後、80℃で3,4’-ジアミノジフェニルエーテル839g(4.19mol)、トルエン839g、フェノール394g(4.19mol)を70℃で溶解した溶解液を6時間かけて間欠滴下した(このとき、3,4’-ジアミノジフェニルエーテル、フェノール、パラホルムアルデヒドのモル比は1:2:4)。その後、82℃で18時間撹拌を行った。ゲル浸透クロマトグラフィーで反応液を上記条件で分析した結果、反応液中に存在する上記化合物(1a)の割合は70.2面積%であった。
反応終了後、撹拌しながら3%水酸化ナトリウム水溶液1800gを30℃にて加えた後、30分撹拌後、静置して水層を分離除去した。その後、油層に撹拌しながら水2200gを30℃で加えた後、30分撹拌後、静置して水層を分離除去した。水の添加から水層の抜き取り工程を4回繰り返した。
得られた油層から、トルエン、フェノールを減圧蒸留によって除去した。蒸留時の温度、圧力は徐々に昇温、減圧し、最終的に90℃、1.5kPaとした。上記化合物(1a)を含む組成物の溶融液を抜き取り、冷却固化後、粉砕し、1383gの上記化合物(1a)含有組成物を得た。
得られた組成物は、1H-NMRと13C-NMRの分析結果から、上記化合物(1a)を含有することを確認した。
また、得られた上記化合物(1a)含有組成物15gを、B型粘度計(TVB-10/東機産業(株)製)を使用して、上記測定条件により測定した100℃における溶融粘度は1.8Pa・Sであった。
実施例1と同様に仕込み、反応、分液工程を経た後、蒸留工程の最終温度を95℃とした。上記化合物(1a)を含む組成物の溶融液を抜き取り、冷却固化後、粉砕し、1280gの上記化合物(1a)含有組成物を得た。
得られた上記化合物(1a)含有組成物について、示差屈折計を検出器とするゲル浸透クロマトグラフィー分析を行った結果、化合物(1a)のピーク面積割合は69.0面積%であり、化合物群(A)のピーク面積割合は11.3面積%であった。このゲル浸透クロマトグラフィー分析のチャートを図2に示す。
また、100℃における溶融粘度は2.7Pa・Sであった。
溶解液を4.5時間かけて間欠滴下したこと以外は実施例1と同様に行い、上記化合物(1a)含有組成物を得た。
得られた上記化合物(1a)含有組成物について、示差屈折計を検出器とするゲル浸透クロマトグラフィー分析を行った結果、化合物(1a)のピーク面積割合は69.4面積%であり、化合物群(A)のピーク面積割合は9.4面積%であった。このゲル浸透クロマトグラフィー分析のチャートを図3に示す。
また、100℃における溶融粘度は、2.0Pa・Sであった。
3,4’-ジアミノジフェニルエーテル、フェノール、パラホルムアルデヒドを1:4:8のモル比で仕込んだこと以外は実施例1と同様に行い、上記化合物(1a)含有組成物を得た。
得られた上記化合物(1a)含有組成物について、示差屈折計を検出器とするゲル浸透クロマトグラフィー分析を行った結果、化合物(1a)のピーク面積割合は72.8面積%であり、化合物群(A)のピーク面積割合は、8.0面積%であった。このゲル浸透クロマトグラフィー分析のチャートを図4に示す。
また、100℃における溶融粘度は、1.5Pa・Sであった。
溶解液を1時間かけて間欠滴下したこと以外は実施例1と同様に行い、上記化合物(1a)含有組成物を得た。
得られた上記化合物(1a)含有組成物について、示差屈折計を検出器とするゲル浸透クロマトグラフィー分析を行った結果、化合物(1a)のピーク面積割合は65.4面積%であり、化合物群(A)のピーク面積割合は14.9面積%であった。このゲル浸透クロマトグラフィー分析のチャートを図5に示す。
また、100℃における溶融粘度は、2.2Pa・Sであった。
溶解液を2時間かけて間欠滴下したこと以外は実施例1と同様に行い、上記化合物(1a)含有組成物を得た。
得られた上記化合物(1a)含有組成物について、示差屈折計を検出器とするゲル浸透クロマトグラフィー分析を行った結果、化合物(1a)のピーク面積割合は68.3面積%であり、化合物群(A)のピーク面積割合は11.6面積%であった。このゲル浸透クロマトグラフィー分析のチャートを図6に示す。
また、100℃における溶融粘度は、2.0Pa・Sであった。
間欠滴下後の反応工程で反応生成水を減圧することにより取り除いた以外は実施例1と同様に行い、上記化合物(1a)含有組成物を得た。
得られた上記化合物(1a)含有組成物について、示差屈折計を検出器とするゲル浸透クロマトグラフィー分析を行った結果、化合物(1a)のピーク面積割合は62.7面積%であり、化合物群(A)のピーク面積割合は11.8面積%であった。このゲル浸透クロマトグラフィー分析のチャートを図7に示す。
また、100℃における溶融粘度は、2.1Pa・Sであった。
温度計、撹拌機、冷却管を備えた4つ口フラスコにフェノール176.3g、3,4’-ジアミノジフェニルエーテル150.0g、トルエン750.0gを仕込み、撹拌下に内温65℃で35%ホルマリン水溶液257.1gを35分かけて滴下した。滴下終了後、常圧下85℃で単蒸留を行い、水、トルエンを留出させ、留出したトルエンはフラスコ内に戻した。さらにフェノール35.3gを追加後、還流下86℃で2時間反応させた。
反応終了後、内温を室温まで下げ、反応混合液に10%水酸化ナトリウム水溶液300gを加えて20分撹拌し、水層を分離除去した。得られた油層にトルエン200gを追加後、3.75%水酸化ナトリウム水溶液800gを加えて20分撹拌して、静置し、水層を分離除去した。
次いで得られた油層に水300gを加えて撹拌し、水層を除去する洗浄操作を6回繰り返した。洗浄した油層を減圧下でトルエンを留去し、上記化合物(1a)含有組成物を185.1g得た。
得られた上記化合物(1a)含有組成物について、示差屈折計を検出器とするゲル浸透クロマトグラフィー分析を行った結果、化合物(1a)のピーク面積割合は61.6面積%であり、化合物群(A)のピーク面積割合は、16.4面積%であった。このゲル浸透クロマトグラフィー分析のチャートを図8に示す。
また、100℃における溶融粘度は、4.7Pa・Sであった。
温度計、撹拌機、冷却管を備えた4つ口フラスコに3,4’-ジアミノジフェニルエーテルを52.5g、フェノール49.5g、92%パラホルムアルデヒド34.5g、トルエン250gを仕込み、90℃で脱水しながら反応させた。その後、110℃に加熱し、トルエンを留去した後、125℃で減圧蒸留により、残留トルエン、未反応物を除去した後、上記化合物(1a)含有組成物を118.2g得た。
得られた上記化合物(1a)含有組成物について、示差屈折計を検出器とするゲル浸透クロマトグラフィー分析を行った結果、化合物(1a)のピーク面積割合は50.0面積%であり、化合物群(A)のピーク面積割合は、20.3面積%であった。このゲル浸透クロマトグラフィー分析のチャートを図9に示す。
また、100℃における溶融粘度は、5.6Pa・Sであった。
溶解液を一気に添加したこと以外は実施例1と同様に行い、上記化合物(1a)含有組成物を得た。
得られた上記化合物(1a)含有組成物について、示差屈折計を検出器とするゲル浸透クロマトグラフィー分析を行った結果、化合物(1a)のピーク面積割合は49.5面積%であり、化合物群(A)のピーク面積割合は29.8面積%であった。このゲル浸透クロマトグラフィー分析のチャートを図10に示す。
また、100℃における溶融粘度は、19.1Pa・Sであった。
下記反応式及び操作に従って、上記化合物(1a)含有組成物を得た。
4つ口フラスコに一般式(4a)で表される化合物280g、酢酸ブチル2290g、酢酸47g(0.7mol)、水490gを仕込み、反応容器内を窒素で置換した後、70℃で2時間撹拌後、静置して水層を分離除去した。その後、油層に撹拌しながら水500gを70℃で加えた後、30分撹拌後、静置して水層を分離除去した。水の添加から水層の抜き取り工程を4回繰り返した。この時の油層のpHは3であった。
得られた油層を40℃に冷却して、40℃を保持しながら35%ホルマリン207g(2.4mol)を30分かけて滴下した後、40℃で5時間撹拌を行った。その後、酢酸ブチルの一部を減圧下90℃で留去し、固形分濃度50%にした。得られた油層を25℃まで徐々に冷却して析出した結晶をろ過した。得られた結晶を、減圧下60℃まで昇温して乾燥し、上記化合物(1a)含有組成物190gを取得した。3,4’-ジアミノジフェニルエーテルに対する収率は68%であった。
1H-NMR(400MHz)測定(溶媒:CDCl3):4.64(s,2H:a),4.66(s,2H:a),5.37(s,2H:b),5.39(s,2H:b),6.53-6.55(ddd,1H:c),6.81-7.35(m,15H:others).
13C-NMR(400MHz)測定(溶媒:CDCl3):50.28(A),50.36(A),79.21(B),80.14(B),108.15(H),110.60(I),112.23(J),114.69(C),117.06(K),120.20(L),120.96(M),126.85(N),126.85(N),127,97(O),128.33(P),129.14(Q),130.20(R),149.90(D),151.27(E),154.38(F),159.06(G).
得られた上記化合物(1a)含有組成物について、示差屈折計を検出器とするゲル浸透クロマトグラフィー分析を行った結果、上記化合物(1a)のピーク面積は92.9面積%であり、化合物群(A)のピーク面積割合は5.3面積%であった。このゲル浸透クロマトグラフィー分析のチャートを図11に示す。
また、100℃における溶融粘度を測定するため、得られた上記化合物(1a)含有組成物を100℃に加熱したが、溶融しなかった。
実施例3と同様の方法により得た上記化合物(1a)含有組成物と、比較例4で得た化合物(1a)含有組成物を溶融混合し、化合物(1a)含有組成物を得た。
得られた上記化合物(1a)含有組成物について、示差屈折計を検出器とするゲル浸透クロマトグラフィー分析を行った結果、化合物(1a)のピーク面積割合は79.7面積%であり、化合物群(A)のピーク面積割合は7.8面積%であった。このゲル浸透クロマトグラフィー分析のチャートを図12に示す。
また、100℃における溶融粘度は、1.4Pa・Sであった。
実施例3と同様の方法により得た上記化合物(1a)含有組成物と、比較例4で得た化合物(1a)含有組成物を実施例8と異なる重量比率で溶融混合し、化合物(1a)含有組成物を得た。
得られた上記化合物(1a)含有組成物について、示差屈折計を検出器とするゲル浸透クロマトグラフィー分析を行った結果、化合物(1a)のピーク面積割合は87.7面積%であり、化合物群(A)のピーク面積割合は4.9面積%であった。このゲル浸透クロマトグラフィー分析のチャートを図13に示す。
また、100℃における溶融粘度は、1.1Pa・Sであった。
また、本発明の具体例ではない比較例4のベンゾオキサジン化合物含有組成物は、100℃では溶融せず、各種成型方法への適用範囲はさらに制限されてしまうことが明らかになった。
これに対して、本発明の具体例である実施例1~9のベンゾオキサジン化合物含有組成物は、化合物群(A)のピーク面積割合が特定の範囲であることにより、当該組成物の100℃における溶融粘度が著しく低くなることが明らかになった。これにより、耐熱性が向上する一般式(1)で表されるベンゾオキサジン化合物が優れた作業性を有すること、フィラー等の添加率を上げることが可能となり放熱性向上に大きく寄与すること、より精密な構造を有する半導体の封止が可能となるため、幅広い用途で利用することができ、非常に有用であることが明らかになった。
上記実施例3により得られた化合物(1a)含有組成物を使用して、各成分を分析するために、GPC-FTIR分析を行った。
(1)GPC-FTIR測定条件
・GPC装置:Prominence HPLC システム(DGU-20A3/LC-20AD/SIL-20AHT/CTO-20A/SPD-20A/RID-10A/CBM-20A)(島津製作所製)
・検出器:示差屈折計(RI検出器)
・FT-IRインターフェース:LC Tranceform 600(Lab Connection製)
・FT-IR:Nicolet iS10(Thermo Scientific製)
・カラム(上流から):Guard ColumnHXL-L+G4000HXL+G3000HXL+G2000HXL×2本(7.8mmID×30cm、東ソー(株)製)・溶離液:THF(富士フイルム和光純薬(株)製HPLC級)
・流速:1.0mL/min.
・試料濃度:2.0mg/mL
・注入量:500μL
・カラム温度:40℃
・測定波数:5000~650cm-1
・分解能:4cm-1
・スキャン回数:8回/1ポイント
(2)試料前処理
試料を秤量し、溶離液を加えて一晩、静置溶解させた。その後、緩やかに振り混ぜ、0.45μmのPTFEカートリッジフィルターでろ過した。目視による不溶解物は確認されなかった。
(3)分子量算出方法
下記の東ソー(株)製標準ポリスチレン(PS)を用いた3次近似曲線を検量線として利用した。従って、示された分子量は標準PS換算分子量となる。
・TSKgel Standard Polystyrene A-500:Nominal Mol.Wt. 5.9×102 Mw/Mn 1.19(0005203/東ソー(株)製)
・TSKgel Standard Polystyrene A-2500:Nominal Mol.Wt. 2.63×103 Mw/Mn 1.05(0005205/東ソー(株)製)
・TSKgel Standard Polystyrene A-5000:Nominal Mol.Wt. 5.06×103 Mw/Mn 1.02(0005206/東ソー(株)製)
・TSKgel Standard Polystyrene F-1:Nominal Mol.Wt. 1.02×104 Mw/Mn 1.02(0005207/東ソー(株)製)
・TSKgel Standard Polystyrene F-2:Nominal Mol.Wt. 1.74×104 Mw/Mn 1.01(0005208/東ソー(株)製)
・TSKgel Standard Polystyrene F-4:Nominal Mol.Wt. 3.79×104 Mw/Mn 1.01(0005209/東ソー(株)製)
RI検出器により得られたクロマトグラム及びピーク位置を、図14に示す。
図14中のピーク7が、化合物(1a)のピークである。
なお、IR感度増大を目的として注入量を増やしたため、ピーク4、ピーク6の分離は不十分であった。
各ピークの平均分子量を下記表1に示す。表1中の「Mn」は数平均分子量を、「Mw」は重量平均分子量を、「Mz」は平均分子量を、「Mw/Mn」は多分散度を意味する。
図14中のピーク1(本発明における分子量が1,000~10,000の範囲にある化合物群(A)を示すピーク)とピーク7(化合物(1a)を示すピーク)のピークトップにおける、FT-IRスペクトルを図15、16に示す。
図15、16のFT-IRスペクトルについて、ベンゼン環C-H伸縮である2849cm-1のピークで規格化したときの2600~3200cm-1の範囲のFT-IRスペクトルを図17に示す。本発明の分子量が1,000~10,000の範囲にある化合物群(A)(ピーク1)は、化合物(1a)(ピーク7)と比べると、3000cm-1付近のピーク強度が弱いという特徴があることが明らかになった。
Claims (5)
- 前記ゲル浸透クロマトグラフィーの測定において、前記一般式(1)で表されるベンゾオキサジン化合物のピーク面積が、検出される全ての成分のピーク面積に対して62面積%~90面積%の範囲である(ただし、前記一般式(1)で表されるベンゾオキサジン化合物のピーク面積、前記化合物群(A)のピーク面積及びその他の検出される成分のピーク面積の総和は100面積%である)、請求項1に記載のベンゾオキサジン化合物含有組成物。
- 請求項1又は2に記載のベンゾオキサジン化合物含有組成物を含む硬化性樹脂組成物。
- 請求項1又は2に記載のベンゾオキサジン化合物含有組成物と、エポキシ樹脂、前記一般式(1)で表されるベンゾオキサジン化合物以外のベンゾオキサジン化合物及びノボラック型フェノール樹脂からなる群より選択される1種以上を含有する、請求項3に記載の硬化性樹脂組成物。
- 請求項3又は4に記載の硬化性樹脂組成物を硬化させてなる硬化物。
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