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WO2023176725A1 - Composé d'éther allylique et son procédé de production, composition de résine durcissable, vernis, préimprégné, produit durci, agent de durcissement de résine d'éther de polyphénylène, et cristaux et leur procédé de production - Google Patents

Composé d'éther allylique et son procédé de production, composition de résine durcissable, vernis, préimprégné, produit durci, agent de durcissement de résine d'éther de polyphénylène, et cristaux et leur procédé de production Download PDF

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Publication number
WO2023176725A1
WO2023176725A1 PCT/JP2023/009336 JP2023009336W WO2023176725A1 WO 2023176725 A1 WO2023176725 A1 WO 2023176725A1 JP 2023009336 W JP2023009336 W JP 2023009336W WO 2023176725 A1 WO2023176725 A1 WO 2023176725A1
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Prior art keywords
formula
carbon atoms
represented
allyl ether
ether compound
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English (en)
Japanese (ja)
Inventor
陽人 那須
建 芳井
佑介 祝田
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Honshu Chemical Industry Co Ltd
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Honshu Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • the present invention relates to an allyl ether compound that can be used as a curing agent that can improve heat resistance, a method for producing the same, a curable resin composition containing the allyl ether compound, a varnish, a prepreg, a cured product, and a polyphenylene ether resin curing agent. and relating to crystals.
  • Polyphenylene ether is known to be suitable as a material for electronic devices such as printed wiring boards because it has a low dielectric constant and a low dielectric loss tangent.
  • Substrate materials for printed wiring boards have long been required to have properties such as flame retardancy and heat resistance.
  • polyphenylene ether resin is classified as a thermoplastic resin, and is generally used in combination with a curing agent.
  • Triallyl isocyanurate which is a general-purpose curing agent, is said to be desirably added in a large amount of 30% by weight or more to polyphenylene ether resin (Non-Patent Document 1), but the curing temperature of polyphenylene ether resin is Since it is volatile at around 150° C., the curing agent volatilizes during thermal curing of polyphenylene ether resin, making it impossible to obtain curing performance equivalent to the added equivalent amount and contaminating the manufacturing equipment.
  • reducing the amount used reduces the heat resistance of the resulting cured product.
  • the present invention provides an allyl ether compound with excellent heat resistance, a curing agent for the allyl ether compound that can improve the heat resistance of the obtained cured polyphenylene ether, and a curable resin composition containing the allyl ether compound. Take it as a challenge.
  • the present inventors discovered that the present inventor has a 2,4,6-triphenyl-1,3,5-triazine skeleton, and added an allyloxy group and a specific substituent to the benzene ring.
  • the allyl ether compound has excellent heat resistance, and by using it as a curing agent for curing polyphenylene ether resin, it is possible to produce a cured product with excellent heat resistance even when used in a smaller amount than conventional curing agents. They found that it can be obtained and completed the present invention.
  • the invention is as follows.
  • Allyl ether compound (1) represented by general formula (1) (In the formula, R 1 is each independently a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, or a cyclic alkyl group having 1 to 6 carbon atoms. Represents a linear or branched alkoxy group, a cyclic alkoxy group having 5 or 6 carbon atoms, or a halogen atom, and n each independently represents 1, 2 or 3.) 2.
  • the allyl ether compound (1) represented by the general formula (1) is any one of formulas (1-1) to (1-9). Allyl ether compound described in. 3.
  • 4-hydroxybenzonitrile (2) represented by general formula (2) is reacted to produce 2,4,6-triphenyl-1, represented by general formula (3).
  • the 2,4,6-triphenyl-1,3,5-triazine derivative (3) obtained in the triazine derivative production step and the allyl halide (4) represented by the general formula (4) are combined in the presence of a basic catalyst. 1.
  • a curable resin composition containing a component (A) a polyphenylene ether resin and a curing agent containing at least an allyl ether compound (1) represented by the general formula (1) as a component (B).
  • R 1 is each independently a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, or a cyclic alkyl group having 1 to 6 carbon atoms.
  • a cured product of the prepreg described in . 11 A polyphenylene ether resin curing agent containing an allyl ether compound (1) represented by general formula (1).
  • R 1 is each independently a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, or a cyclic alkyl group having 1 to 6 carbon atoms. Represents a linear or branched alkoxy group, a cyclic alkoxy group having 5 or 6 carbon atoms, or a halogen atom, and n each independently represents 1, 2 or 3.
  • a crystal of a compound represented by formula (1-1) having a melting point in the range of 186 to 192°C. 13.
  • the allyl ether compound (1) represented by the general formula (1) of the present invention has a very high 5% weight loss temperature and excellent heat resistance. This is extremely beneficial in terms of yield and manufacturing efficiency, as it can reduce problems such as equipment contamination caused by oxidation. Furthermore, a cured product formed into a film using the compound together with a polyphenylene ether resin has a high glass transition temperature (Tg) and excellent heat resistance, so it can be used as a curing agent that can improve heat resistance. Furthermore, even if the amount used is less than that of conventional curing agents, a cured product with excellent physical properties can be obtained. It is extremely useful industrially as it can significantly reduce the Tg glass transition temperature (Tg) and excellent heat resistance, so it can be used as a curing agent that can improve heat resistance. Furthermore, even if the amount used is less than that of conventional curing agents, a cured product with excellent physical properties can be obtained. It is extremely useful industrially as it can significantly reduce the amount of the amount used is less than that of conventional curing agents, a
  • FIG. 1 is a diagram showing a chart of powder X-ray diffraction (PXRD) measurement of crystals of compound (1-1) obtained in Example 1.
  • FIG. 1 is a diagram showing a chart of powder X-ray diffraction (PXRD) measurement of crystals of compound (1-1) obtained in Example 1.
  • FIG. 1 is a diagram showing a chart of powder X-ray diffraction (PXRD) measurement of crystals of compound (1-1) obtained in Example 1.
  • PXRD powder X-ray diffraction
  • the compound of the present invention is an allyl ether compound (1) represented by general formula (1).
  • R 1 each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, or a cyclic alkyl group having 1 to 6 carbon atoms.
  • a linear or branched alkyl group having 1 to 4 carbon atoms a cyclic alkyl group having 5 or 6 carbon atoms, a linear or branched alkoxy group having 1 to 4 carbon atoms, It is preferably a cyclic alkoxy group having 5 or 6 carbon atoms, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cyclic alkyl group having 5 or 6 carbon atoms. It is more preferably either a linear or branched alkyl group having 1 to 4 carbon atoms, and it is an alkyl group having 1 carbon atom, that is, a methyl group. It is particularly preferable.
  • n in general formula (1) each independently represents 1, 2 or 3. Among these, 2 or 3 is preferable. When n in general formula (1) is 2 or 3, it is preferable that the substituent positions are at two ortho positions of the allyloxy group.
  • allyl ether compound (1) represented by the general formula (1) of the present invention include compounds represented by the formulas (1-1) to (1-9) (hereinafter, compounds (1- 1) etc.) Among these, compounds represented by formula (1-1), formula (1-4), formula (1-5), formula (1-7) or formula (1-9) are preferred; ), formula (1-4), formula (1-5) or formula (1-9) are more preferred; ) are more preferred, and compounds represented by formula (1-1) are particularly preferred.
  • the compound represented by formula (1-1) can be handled as a crystalline solid and has excellent handling properties. , very useful.
  • the melting point of such crystals is preferably in the range of 186-192°C, more preferably in the range of 187-191°C.
  • This crystal has diffraction peaks at diffraction angles 2 ⁇ of 14.3 ⁇ 0.2°, 15.7 ⁇ 0.2°, and 20.3 ⁇ 0.2° in the powder X-ray diffraction peak pattern using Cu-K ⁇ rays. It is preferable to have.
  • this crystal preferably has peaks at diffraction angles 2 ⁇ of 10.3 ⁇ 0.2° and 21.4 ⁇ 0.2°, and furthermore preferably has peaks at diffraction angles 2 ⁇ of 12.3 ⁇ 0.2° and 21.4 ⁇ 0.2°. It is particularly preferred to have peaks at 0.2° and 19.3 ⁇ 0.2°. It is preferable that the relative integrated intensity of these diffraction peaks is 10 or more, but the relative integrated intensity may vary depending on the measuring device and conditions, or if it is a mixture with other crystals. , the crystalline phase can be identified based on the usual analysis method of powder X-ray diffraction analysis. Furthermore, the compound represented by formula (1-5) can be handled as a crystalline solid and has excellent handling properties, so it is very useful.
  • the melting point of such crystals is preferably in the range of 160-178°C, more preferably in the range of 163-175°C. It may have two melting points in the range of 160 to 168 °C and 170 to 178 °C, and this embodiment is more preferable, and it may have two melting points in the range of 163 to 166 °C and 171 to 175 °C. is particularly preferred.
  • the melting point can be measured as an onset temperature measured using a differential scanning calorimeter. The onset temperature means the temperature at the intersection of the tangent at the inflection point on the low temperature side of the endothermic peak of differential scanning calorimetry and the extension of the baseline.
  • the allyl ether compound (1) represented by the general formula (1) of the present invention can be used as a curing agent for polyphenylene ether resin, and since it has an allyloxy group, it can be used as a raw material for bismaleimide resin, and as a polythiol compound. It can be used as a raw material for a curable resin that is cured by a reaction with enethiol.
  • allyl ether compound (1) represented by the general formula (1) of the present invention there are no particular limitations on the starting materials and production method for its production.
  • 4-hydroxybenzonitrile (2) represented by general formula (2) is reacted in the presence of trifluoromethanesulfonic acid to form a compound represented by general formula (3).
  • allyl etherification step in which the allyl halide (4) represented by the general formula (4) is subjected to a condensation reaction in the presence of a basic catalyst, to obtain the desired general formula (1).
  • a manufacturing method for obtaining the allyl ether compound (1) shown below is mentioned. (In the formula, X represents a halogen atom, and R 1 and n are the same as defined in general formula (1).)
  • the method for producing the 2,4,6-triphenyl-1,3,5-triazine derivative (3) from the 4-hydroxybenzonitrile (2) in the above reaction formula is known. For example, it can be synthesized according to the method described in Organic Letters, Vol. 18, No. 14, pp. 3394-3397, 2016. In the triazine derivative production step, it is preferable to use trifluoromethanesulfonic acid because the 2,4,6-triphenyl-1,3,5-triazine derivative (3) can be obtained with improved yield. If the 2,4,6-triphenyl-1,3,5-triazine derivative (3) can be obtained with improved yield, the allyl ether compound (1) represented by the general formula (1) of the present invention can be produced with excellent yield.
  • the amount of trifluoromethanesulfonic acid used is preferably in the range of 1 to 5 equivalents (times the weight), and 2 to 4 equivalents, based on the 4-hydroxybenzonitrile (2).
  • the amount is more preferably within the range of 2.5 to 3.5 equivalents, and even more preferably 2.5 to 3.5 equivalents.
  • the temperature in the reaction system during addition of trifluoromethanesulfonic acid is preferably in the range of 0 to 5°C, and thereafter preferably in the range of 20 to 30°C.
  • the triazine derivative production step of the reaction to obtain the 2,4,6-triphenyl-1,3,5-triazine derivative (3) from the 4-hydroxybenzonitrile (2) 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, and examples thereof include halogenated hydrocarbon solvents such as dichloromethane and chloroform.
  • the amount used is not particularly limited as long as it does not interfere with the reaction, but it is usually in the range of 1 to 50 times, preferably 1 to 40 times, more preferably 1 to 40 times the weight of 4-hydroxybenzonitrile (2). It is used in a range of ⁇ 30 times the weight.
  • 4-hydroxybenzonitrile (2) represented by the general formula (2) include compounds represented by the formulas (2-1) to (2-9) (hereinafter, compounds (2- 1) etc.) Among these, compounds represented by formula (2-1), formula (2-4), formula (2-5), formula (2-7) or formula (2-9) are preferred; ), formula (2-4), formula (2-5) or formula (2-9) are more preferable, and formula (2-1), formula (2-5) or formula (2-9) is more preferred. ) are more preferred, and compounds represented by formula (2-1) are particularly preferred.
  • 2,4,6-triphenyl-1,3,5-triazine derivative (3) represented by general formula (3) include those represented by formulas (3-1) to (3-9).
  • Examples include compounds (hereinafter sometimes referred to as compound (3-1) etc.).
  • compounds represented by formula (3-1), formula (3-4), formula (3-5), formula (3-7) or formula (3-9) are preferred;
  • formula (3-4), formula (3-5) or formula (3-9) are more preferred;
  • compounds represented by formula (3-1) are particularly preferred.
  • the compound represented by formula (3-5) can be crystallized from a solution using a ketone solvent, such as methyl isobutyl ketone, as a crystal with a melting point in the range of 250 to 254°C. Obtainable.
  • the allyl halide (4) represented by formula (4) is not particularly limited, and usually allyl chloride, allyl bromide, allyl iodide, etc. are preferably used, but allyl chloride or allyl bromide is particularly preferably used. It will be done.
  • the amount of allyl halide (4) represented by general formula (4) used is one hydroxy group of the 2,4,6-triphenyl-1,3,5-triazine derivative (3). It is preferably in the range of 1 to 10 equivalents, more preferably in the range of 1 to 5 equivalents, even more preferably in the range of 1 to 3 equivalents.
  • a basic catalyst in order to capture the generated hydrogen halide.
  • a basic catalyst include inorganic bases such as sodium hydride, sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide, as well as alkali metal bromides such as sodium bromide and potassium bromide, if necessary.
  • the reaction may be carried out in the presence of a cocatalyst such as a salt, an alkali metal iodide salt such as sodium iodide or potassium iodide, or ammonium bromide or ammonium iodide.
  • the basic catalyst and co-catalyst are not limited to these.
  • the amount of the basic catalyst used is preferably in the range of 1 to 10 equivalents per hydroxy group of the 2,4,6-triphenyl-1,3,5-triazine derivative (3), The range is preferably 1 to 5 equivalents, and even more preferably 1 to 3 equivalents.
  • the reaction to obtain the target allyl ether compound (1) represented by the general formula (1) from the 2,4,6-triphenyl-1,3,5-triazine derivative (3) is usually carried out in the presence of a solvent. It will be held on. The same applies to the etherification step.
  • the solvent is not particularly limited as long as it does not inhibit the reaction, but examples include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and sec-butyl alcohol; Cyclic alkanes such as cyclopentane, cyclohexane, and cycloheptane, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane, ketones such as acetone, diethyl ketone, methyl-n-butyl ketone, and methyl isobutyl ketone, ethyl acetate, and n-propyl acetate.
  • alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and sec-buty
  • esters such as isopropyl acetate, n-butyl acetate, and isobutyl acetate, nitriles such as acetonitrile, and amides such as N,N-dimethylformamide and N-methylpyrrolidone.
  • solvents can be used alone or in combination.
  • the amount of solvent used is not particularly limited as long as it does not interfere with the reaction, but it is usually 0.5 to 5 times the weight of the 2,4,6-triphenyl-1,3,5-triazine derivative (3). The amount is preferably 1 to 3 times the weight.
  • the reaction temperature is usually carried out in the range of 0 to 120°C, preferably in the range of 10 to 80°C, and more preferably in the range of 20 to 70°C. If the reaction temperature is too high, by-products will increase and the yield will decrease; if the reaction temperature is too low, the reaction rate will be slow.
  • the reaction may be carried out under normal pressure conditions, or may be carried out under increased pressure or reduced pressure.
  • the target allyl ether compound (1) represented by the general formula (1) can be obtained from the obtained reaction mixture by a known method.
  • the remaining raw materials and solvent are distilled off from the reaction mixture to obtain the target product as a residual liquid, and the allyl ether compound is separated from water, dissolved in a solvent, and washed with water.
  • an allyl ether compound can be obtained through a crystallization step.
  • Crystals of the compound (1-1) of the present invention can be obtained by adding water to a solution containing an allyl ether compound represented by formula (1-1) and a ketone such as acetone, methyl ethyl ketone, methyl-n-butyl ketone, or methyl isobutyl ketone. It can be obtained by mixing and crystallizing.
  • a ketone such as acetone, methyl ethyl ketone, methyl-n-butyl ketone, or methyl isobutyl ketone.
  • Specific examples of the ketone are as described above, and among these ketones, linear ketones having 3 to 6 carbon atoms are preferred, and acetone is particularly preferred.
  • the amount of ketone to be used with respect to the allyl ether compound represented by formula (1-1) is in the range of 1 to 10 times by weight, preferably in the range of 2 to 8 times by weight.
  • the amount of water to be used is in the range of 0.5 to 10 times by weight, preferably 1 to 6 times by weight.
  • Water acts as a poor solvent in which the allyl ether compound represented by formula (1-1) is difficult to dissolve. Since this method for producing crystals uses water, it has the advantage that impurities such as water-soluble salts, metals, and water-soluble raw materials can be removed from the filtrate when filtering the crystals.
  • the temperature at which crystals are precipitated is preferably in the range of 20 to 70°C, more preferably in the range of 20 to 60°C, even more preferably in the range of 20 to 55°C.
  • the filtered crystals are preferably washed with the ketone and/or water used to precipitate the crystals.
  • Crystals of the compound (1-5) of the present invention can be obtained by crystallization from a solution containing an allyl ether compound represented by formula (1-5) and an aromatic hydrocarbon solvent such as toluene or xylene.
  • aromatic hydrocarbon solvent such as toluene or xylene.
  • Specific examples of the aromatic hydrocarbon solvent are as described above, and among these, aromatic hydrocarbon solvents having 6 to 9 carbon atoms are preferable, and aromatic hydrocarbon solvents having 7 or 8 carbon atoms are preferable. is more preferred, and toluene is particularly preferred.
  • the amount of aromatic hydrocarbon solvent used relative to the allyl ether compound represented by formula (1-5) is in the range of 1 to 10 times by weight, preferably in the range of 2 to 8 times by weight.
  • the temperature at which crystals are precipitated is preferably in the range of 20 to 70°C, more preferably in the range of 20 to 60°C, even more preferably in the range of 20 to 55°C.
  • the filtered crystals are preferably washed from the aromatic hydrocarbon solvent used to precipitate the crystals.
  • the triazine derivative production step, the allyl etherification step, and other neutralization, distillation, crystallization, filtration, and drying steps involved in this production method may cause oxidative deterioration, coloring, and electrostatic ignition due to volatile solvents. It is preferable to carry out the reaction under an inert gas atmosphere such as nitrogen or argon, which contains less oxygen as a causative agent.
  • the polyphenylene ether resin curing agent of the present invention contains the allyl ether compound (1) represented by the general formula (1), heat resistance is improved even though the amount used is extremely smaller than that of conventional curing agents.
  • the 5% weight loss temperature is high, problems such as equipment contamination due to volatilization of the curing agent can be reduced.
  • the amount used can be reduced, the content of resin base materials with low dielectric constant and dielectric loss tangent, such as polyphenylene ether resin, can be increased compared to conventional curable resin compositions.
  • the amount used can be reduced, the content of resin base materials with low dielectric constant and dielectric loss tangent, such as polyphenylene ether resin, can be increased compared to conventional curable resin compositions.
  • allyl ether compound (1) represented by general formula (1) may be used, or two or more types may be used in combination.
  • the polyphenylene ether resin curing agent preferably contains only the allyl ether compound (1) represented by the general formula (1), but the allyl ether compound (1) represented by the general formula (1) may be Other curing agents other than the ether compound (1) may be included. Examples of such curing agents include trialkenyl isocyanurate compounds, polyfunctional allyl ether compounds having two or more allyl ether groups in the molecule other than the allyl ether compound (1) represented by general formula (1), and molecules. Examples include polyfunctional acrylate compounds, polyfunctional methacrylate compounds, and polyfunctional vinyl compounds having two or more acrylic groups therein.
  • the curable resin composition of the present invention contains a polyphenylene ether resin as component (A), and the polyphenylene ether resin that can be used is not particularly limited.
  • specific examples of such polyphenylene ether resins include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2- methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), 2,6-dimethylphenol and other phenols (e.g.
  • polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols, bisphenols, or trisphenols 2,6- Examples include polyphenylene ether copolymers obtained by coupling dimethylphenol and other phenols with biphenols, bisphenols, or trisphenols.
  • a polyphenylene ether in which the terminal hydroxyl group of the polyphenylene ether resin is modified with a functional group having an unsaturated double bond such as allyl ether, acryloyl, methacryloyl, vinyl ether, etc.
  • An acrylated product of polyphenylene ether which is a copolymer of 6-dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, is preferred.
  • the curable resin composition of the present invention contains at least an allyl ether compound (1) represented by the general formula (1) as a component (B) as a curing agent.
  • allyl ether compounds (1) represented by general formula (1) one type may be used, or two or more types may be used in combination. It is preferable that the curing agent of component (B) contains only the allyl ether compound (1) represented by the general formula (1), but within the range that does not impair the effects of the present invention, Other curing agents other than the allyl ether compound (1) may be included.
  • curing agents examples include trialkenyl isocyanurate compounds, polyfunctional allyl ether compounds having two or more allyl ether groups in the molecule other than the allyl ether compound (1) represented by general formula (1), and molecules.
  • examples include polyfunctional acrylate compounds, polyfunctional methacrylate compounds, and polyfunctional vinyl compounds having two or more acrylic groups therein.
  • the content of component (B) in the curable resin composition of the present invention is preferably in the range of 1.0 to 10.0 parts by weight, and preferably 2.0 to 10.0 parts by weight, based on 100 parts by weight of component (A). It is more preferably in the range of 8.0 parts by weight, even more preferably in the range of 3.6 to 7.0 parts by weight, and particularly preferably in the range of 4.0 to 6.0 parts by weight.
  • the curable resin composition of the present invention preferably contains a reaction initiator as component (C) in addition to component (A) and component (B).
  • Component (C) is added to promote the crosslinking reaction of the curable resin composition containing component (A) and component (B).
  • Component (C) is not particularly limited as long as it promotes the crosslinking reaction, and examples thereof include imidazoles, tertiary amines, quaternary ammonium salts, boron trifluoride amine complexes, and organophosphines.
  • ionic catalysts such as organophosphonium salts, organic peroxides, hydroperoxides, radical polymerization initiators such as azoisobutyronitrile, and the like.
  • organic peroxides include di-t-butyl peroxide, dilauroyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,2-bis(t-butyl peroxide).
  • fats such as oxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne, di-n-propylperoxydicarbonate, etc.
  • Group organic peroxides dibenzoyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-amyl peroxybenzoate, t-butylcumyl peroxide, bis(1-t-butylperoxy-1-methylethyl) ) benzene, 2-phenyl-2-[(2-phenylpropan-2-yl)peroxy]propane, ⁇ , ⁇ '-di(t-butylperoxy)diisopropylbenzene, ⁇ , ⁇ '-bis(t-butyl Examples include aromatic organic peroxides containing an aromatic ring, such as peroxy-m-isopropyl)benzene and di-t-butylperoxyisophthalate.
  • aromatic organic peroxides examples include dicumyl peroxide, t-butylcumyl peroxide, bis(1-t-butylperoxy-1-methylethyl)benzene, 2-phenyl-2-[(2-phenylpropane- 2-yl)peroxy]propane is more preferred, and 2-phenyl-2-[(2-phenylpropan-2-yl)peroxy]propane is particularly preferred.
  • the curable resin composition of the present invention preferably contains component (C) in an amount of 0.05 to 0.9% by weight based on the total amount of the curable resin composition, and preferably 0.15 to 0.8% by weight. %, more preferably 0.3 to 0.7% by weight, particularly preferably 0.35 to 0.6% by weight.
  • Component (C) may be used alone or in combination of two or more.
  • the curable resin composition of the present invention preferably contains a filler as component (D) in addition to component (A), component (B), and optionally component (C). It is preferable to contain component (D) in a range of 10 to 150 parts by weight, more preferably in a range of 10 to 100 parts by weight, based on 100 parts by weight of the curable resin composition.
  • Component (D) is not particularly limited as long as it is a filler that is normally used in curable resin compositions, and includes, for example, silicon oxide, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, silicon nitride, Inorganic fillers such as silicon carbide and hexagonal boron nitride can be used in combination.
  • the curable resin composition of the present invention may contain a solvent as component (E), and is particularly preferably in the form of a varnish in which component (E) is dissolved or dispersed.
  • Component (E) is not particularly limited as long as it dissolves or disperses the curable resin composition of the present invention, and examples thereof include aromatic compounds such as toluene and xylene, methyl ethyl ketone, cyclopentanone, and cyclohexanone. Examples include ketone compounds and chlorine organic solvents such as chloroform.
  • aromatic compounds such as toluene and xylene, ketone compounds such as methyl ethyl ketone, cyclopentanone, and cyclohexanone are preferred, aromatic compounds such as toluene and xylene are more preferred, and toluene is particularly preferred.
  • component (E) in a range of 50 to 200 parts by weight, more preferably in a range of 70 to 150 parts by weight, based on 100 parts by weight of the curable resin composition.
  • the method for preparing the curable resin composition of the present invention is not particularly limited, and includes, for example, a method in which the above-mentioned components are mixed and mixed or dispersed using a stirrer.
  • the prepreg of the present invention comprises a curable resin composition containing component (A) and component (B), optionally containing component (C) and further component (D), and a reinforcing component (F). It can be obtained by mixing it with fibers.
  • the mixing method include a method of applying a varnish containing a curable resin composition to the reinforcing fiber as component (F), a method of impregnating the reinforcing fiber, and the like.
  • Component (F) in the present invention is not particularly limited as long as it is a reinforcing fiber that is normally used in prepregs, and examples include carbon fiber, aramid fiber, nylon fiber, high-strength polyester fiber, glass fiber, boron fiber, Various inorganic fibers or organic fibers such as alumina fibers and silicon nitride fibers can be used. Among these, from the viewpoint of specific strength and specific elasticity, carbon fibers, aramid fibers, glass fibers, boron fibers, alumina fibers, and silicon nitride fibers may be mentioned. Among these, carbon fiber is preferred from the viewpoint of mechanical properties and weight reduction.
  • the thickness of the fiber base material is preferably 0.3 mm or less, more preferably 0.15 mm or less, and even more preferably 0.1 mm or less.
  • Component (F) may be used alone or in combination of two or more.
  • the cured product in the present invention can be obtained by curing the curable resin composition of the present invention.
  • the method for producing the cured product of the present invention includes, for example, a film of a curable resin composition formed by casting a varnish onto a support such as a polyimide or polyester film or a glass substrate and drying it, or a film of the above-mentioned prepreg.
  • the heat curing temperature can be appropriately determined within the range of 105 to 270°C.
  • the analysis method in the present invention is as follows. ⁇ Analysis method> (1) Purity analysis (area percentage) Measuring device: High performance liquid chromatography analyzer Prominence UFLC/manufactured by Shimadzu Corporation Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A Column: HALO-C18 (inner diameter 3mm, length 75mm) Oven temperature: 50°C Flow rate: 0.7mL/min.
  • Example 1 (a) Synthesis of compound (3-1) 1.0 g of 4-hydroxy-3,5-dimethylbenzonitrile (compound (2-1)) and 30 g of dichloromethane were charged into a two-necked flask containing a stirring bar, and the inside of the system was purged with nitrogen by bubbling nitrogen. Thereafter, the flask was placed in an ice bath (0 to 1°C) prepared on a magnetic stirrer, stirred while maintaining a nitrogen atmosphere, and 3.0 g of trifluoromethanesulfonic acid was added using a dropping funnel over 10 minutes. . After the addition, the mixture was stirred at room temperature for 20 hours.
  • the target substance in the reaction solution after stirring was 97.5% (HPLC area %).
  • water was added to the reaction solution, the solution was transferred to a separatory funnel, methyl isobutyl ketone (MIBK) was added, and the mixture was shaken to perform a liquid separation operation. Thereafter, the obtained oil layer was washed with 10% NaHCO 3 water, phosphoric acid was added to adjust the pH, and the aqueous layer was separated. The obtained oil layer was dried under reduced pressure using an evaporator to obtain crystals. The appearance was an orange powder, the purity was 97.4% (HPLC area %), and the yield was 1.2 g.
  • Example 2 (a) Synthesis of compound (3-5) 1.0 g of 4-hydroxy-3-methoxybenzonitrile (compound 2-5) and 30 g of dichloromethane were placed in a 100 mL test tube containing a stirrer, and the inside of the system was purged with nitrogen by nitrogen bubbling. Thereafter, the test tube was placed in an ice bath (0 to 6°C) prepared on a magnetic stirrer, stirred while maintaining a nitrogen atmosphere, and 3.0 g of trifluoromethanesulfonic acid was added. After the addition, the mixture was stirred at room temperature for 82 hours. The target substance in the reaction solution after stirring was 73.3% (HPLC area %).
  • the reaction solution was transferred to a separatory funnel, methyl isobutyl ketone (MIBK) and water were added, and the mixture was shaken to perform a liquid separation operation. Thereafter, the obtained oil layer was washed with 8% NaHCO 3 water, phosphoric acid was added to adjust the pH, and the aqueous layer was separated. The obtained oil layer was dried under reduced pressure using an evaporator to obtain crystals. The appearance was a red powder, the purity was 92.9% (HPLC area %), and the yield was 0.6 g.
  • MIBK methyl isobutyl ketone
  • the target substance in the reaction solution after stirring was 89.0% (HPLC area %).
  • toluene and water were added to perform a liquid separation operation. Thereafter, the temperature of the water bath was lowered to perform crystallization, and the precipitated crystals were filtered off using Kiriyama filtration and dried using an evaporator.
  • the appearance was a white powder, the purity was 96.6% (HPLC area %), and the yield was 0.2 g.
  • reaction solution was transferred to a separatory funnel, methyl isobutyl ketone (MIBK) and water were added, and the mixture was shaken to perform a liquid separation operation.
  • MIBK methyl isobutyl ketone
  • the obtained oil layer was dried under reduced pressure using an evaporator to obtain crystals of compound (3-9). The appearance was a pale yellow powder with a purity of 72.7% (HPLC area %).
  • Component (A) is an acrylate of polyphenylene ether, which is a copolymer of 2,6-dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane (hereinafter referred to as PPE resin A).
  • PPE resin A acrylate of polyphenylene ether, which is a copolymer of 2,6-dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane
  • a varnish was prepared by adding 0.68 parts by weight of dicumyl peroxide (manufactured by NOF Corporation, trade name: "Percumil D”), which is a peroxide, at room temperature using a magnetic stirrer.
  • the prepared varnish was applied to a thickness of 0.2 cm on a 20 cm square polyimide film (manufactured by Ube Industries, Ltd., trade name "Upilex”) and dried at room temperature.
  • a semi-cured product of the curable resin composition was obtained by drying and removing the solvent remaining on the coating film of the curable resin composition at 105° C. for 1 hour using a vacuum dryer.
  • Example 5 Except that the amount of compound (1-1) used in Example 4 was 3.6 parts by weight (Example 5), 4.0 parts by weight (Example 6), and 6.0 parts by weight (Example 7).
  • Example 5 Except that the amount of compound (1-1) used in Example 4 was 3.6 parts by weight (Example 5), 4.0 parts by weight (Example 6), and 6.0 parts by weight (Example 7).
  • Example 5 Except that the amount of compound (1-1) used in Example 4 was 3.6 parts by weight (Example 5), 4.0 parts by weight (Example 6), and 6.0 parts by weight (Example 7).
  • Example 7 A resin film was prepared in the same manner as in Example 4, and its heat resistance was evaluated. The results are summarized in Table 3.
  • the cured product formed into a film using compound (1-1), which is the compound of the present invention, together with polyphenylene ether resin has a high glass transition temperature (Tg) of 184 to 198°C, and has excellent heat resistance. became clear.
  • triallyl isocyanurate which is a general-purpose curing agent, is said to be preferably added in a large amount to polyphenylene ether resin, but compound (1-1), which is a compound of the present invention, can be used in a small amount.
  • the allyl ether compound (1) represented by the general formula (1) of the present invention can be used in an extremely small amount compared to conventional curing agents, and even when the amount used is reduced, it has excellent physical properties. It has become clear that the cost of the curing agent can be significantly reduced in the production of processed products using polyphenylene ether resin, and that it is very useful industrially.

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Abstract

Le problème à résoudre par la présente invention est de fournir un composé d'éther allylique ayant une excellente résistance à la chaleur, un agent de durcissement pour un composé d'éther allylique pouvant améliorer la résistance à la chaleur d'un produit durci obtenu, et une composition de résine durcissable, etc. contenant le composé d'éther allylique. La solution selon l'invention porte sur un composé d'éther allylique (1) représenté par la formule générale (1). (Dans la formule, R1 représentent chacun indépendamment un groupe alkyle linéaire ou ramifié en C1-6, un groupe alkyle cyclique en C5 ou C6, un groupe alcoxy linéaire ou ramifié en C1-6, un groupe alcoxy cyclique en C5 ou C6, ou un atome d'halogène, et n représentent chacun indépendamment 1, 2 ou 3.)
PCT/JP2023/009336 2022-03-16 2023-03-10 Composé d'éther allylique et son procédé de production, composition de résine durcissable, vernis, préimprégné, produit durci, agent de durcissement de résine d'éther de polyphénylène, et cristaux et leur procédé de production Ceased WO2023176725A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017170183A1 (fr) * 2016-03-31 2017-10-05 株式会社Adeka Composition et nouveau composé
WO2017170182A1 (fr) * 2016-03-31 2017-10-05 株式会社Adeka Composition photosensible et nouveau composé

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017170183A1 (fr) * 2016-03-31 2017-10-05 株式会社Adeka Composition et nouveau composé
WO2017170182A1 (fr) * 2016-03-31 2017-10-05 株式会社Adeka Composition photosensible et nouveau composé

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KOTHA SAMBASIVARAO, SOLANKE BALAJI.U., GUPTA NAVEEN KUMAR: "Design and synthesis of C3-symmetric molecules containing oxepine and benzofuran moieties via Metathesis", JOURNAL OF MOLECULAR STRUCTURE, ELSEVIER AMSTERDAM, NL, vol. 1244, 1 November 2021 (2021-11-01), NL , pages 130907, XP093092746, ISSN: 0022-2860, DOI: 10.1016/j.molstruc.2021.130907 *

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