WO2020017141A1 - Diluant réactif, composition, matériau d'étanchéité, produit durci, substrat, composant électronique, composé époxy et procédé de production de composé - Google Patents

Diluant réactif, composition, matériau d'étanchéité, produit durci, substrat, composant électronique, composé époxy et procédé de production de composé Download PDF

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Publication number
WO2020017141A1
WO2020017141A1 PCT/JP2019/019696 JP2019019696W WO2020017141A1 WO 2020017141 A1 WO2020017141 A1 WO 2020017141A1 JP 2019019696 W JP2019019696 W JP 2019019696W WO 2020017141 A1 WO2020017141 A1 WO 2020017141A1
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Prior art keywords
compound
component
composition
cured product
epoxy
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PCT/JP2019/019696
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English (en)
Japanese (ja)
Inventor
務 高嶋
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Ｊｘｔｇエネルギー株式会社
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Priority to KR1020217000729A priority Critical patent/KR20210032383A/ko
Priority to JP2020530910A priority patent/JPWO2020017141A1/ja
Priority to CN201980047141.XA priority patent/CN112424255A/zh
Publication of WO2020017141A1 publication Critical patent/WO2020017141A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/36—Epoxy compounds containing three or more epoxy groups together with mono-epoxy compounds
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds

Definitions

  • the present invention relates to a reactive diluent, a composition, a sealing material, a cured product, a substrate, an electronic component, an epoxy compound, an intermediate in the production of the epoxy compound, a method for producing the intermediate, and a method for producing the epoxy compound.
  • This application claims priority based on Japanese Patent Application No. 2018-134435 and Japanese Patent Application No. 2018-134436 for which it applied to Japan on July 17, 2018, and uses the content here.
  • Epoxy resin compositions have excellent electrical performance and adhesive strength, and are widely used as interlayer insulating materials for printed circuit boards of electrical and electronic equipment, sealing materials, matrix materials for various structural members, adhesives, etc. I have.
  • current electronic devices are required to be able to transmit and receive high-speed and large-volume information.
  • the delay between transmissions of electric signals increases due to the large inter-wiring capacity of the conventional interlayer insulating material, and the transmission and reception of high-speed and large-capacity information is performed. Was hindered. Since the delay time is proportional to the capacitance between the wirings, if the capacitance between the wirings is reduced by lowering the dielectric of the interlayer insulating material, the speed of transmission of the electric signal can be increased.
  • dielectric loss tangent and relative dielectric constant Two characteristics, dielectric loss tangent and relative dielectric constant, are important as dielectric characteristics.
  • a method of lowering the dielectric constant of an epoxy resin a method of increasing the amount of silica filler is known.
  • the dielectric loss tangent can be reduced, but there is a problem that the dielectric constant increases.
  • Epoxy resin compositions are widely used in various applications because of their excellent adhesiveness and electromechanical properties. Epoxy resin compositions are usually provided with preferable characteristics according to the use by adding various additives. For example, when an epoxy resin composition is used as a semiconductor encapsulant, with the recent miniaturization of electronic devices, it is necessary to fill the encapsulant into minute gaps. It has been demanded. As a means for reducing the viscosity of a high-viscosity resin composition, a diluent is used. Diluents are divided into non-reactive and reactive.
  • the reactive diluent reacts with the resin component of the resin composition and cures together with the resin composition to become a part of a cured product, there is an advantage that the diluent component hardly bleeds out.
  • a reactive diluent for lowering the viscosity of the resin composition and exhibiting excellent dielectric properties for example, a compound in which a glycidyl group is bonded to an isostearic acid raw material via an ester bond as described in Non-Patent Document 1 ( (Product name: FOLDI) is disclosed.
  • the epoxy resin composition When the epoxy resin composition is used as a cured product, the cured product becomes rigid due to its high modulus of elasticity, and thermal expansion and curing shrinkage occur to easily apply stress to peripheral members. As a result, a dimensional deviation or a crack may cause a malfunction. For this reason, a material that is flexible when cured is required.
  • the present invention has been made to solve the above-described problems, and has realized a reduction in the viscosity of a resin composition, and a cured product of the resin composition has realized low dielectric properties and flexibility. It is an object of the present invention to provide a novel reactive diluent capable of satisfying the above requirement. Another object of the present invention is to provide a composition containing the reactive diluent. Another object of the present invention is to provide a sealing material containing the composition. Another object of the present invention is to provide a cured product of the composition. Another object of the present invention is to provide a substrate including the cured product. Another object of the present invention is to provide an electronic component including the cured product.
  • a composition comprising the following components A and B, Component A: a compound represented by the following general formula (1), (In the formula (1), n is 0 or 1.)
  • Component B a compound having two or more groups containing an epoxy ring in the molecule.
  • a sealing material containing the composition according to [3] or [4].
  • a substrate comprising the cured product according to [6].
  • An electronic component comprising the cured product according to [6].
  • a method for producing a compound represented by the following general formula (2), comprising obtaining a compound represented by the following general formula (2) by hydroxylating a compound represented by the following general formula (3): .
  • the low viscosity of a resin composition is implement
  • a composition containing the reactive diluent can be provided.
  • a sealing material containing the composition can be provided.
  • a cured product of the composition can be provided.
  • a substrate provided with the cured product can be provided.
  • an electronic component including the cured product can be provided.
  • the present invention it is possible to provide a novel epoxy compound that realizes a low viscosity of a resin composition and achieves a low dielectric property and imparts flexibility in a cured product of the resin composition.
  • an intermediate in the production of the epoxy compound can be provided.
  • a method for producing the intermediate can be provided.
  • a method for producing the epoxy compound can be provided.
  • the compound according to the embodiment of the present invention is a compound represented by the following general formula (1) (may be abbreviated as “compound (1)”).
  • n 0 or 1.
  • the viscosity of the resin composition when compounded into a resin composition, the viscosity of the resin composition is reduced, and the cured product of the resin composition achieves low dielectric properties and imparts flexibility. Achievable.
  • Compound (1) has a structure of a saturated hydrocarbon in the molecule. Therefore, when it is blended with the resin composition, it is considered that the cured product contributes to exhibiting low dielectric properties.
  • Compound (1) has a branched saturated hydrocarbon structure in the molecule. Therefore, it is considered that when it is mixed with the resin composition, it contributes to lowering the viscosity of the resin composition. In addition, it is considered that this structure contributes to imparting flexibility to the cured product when blended with the resin composition.
  • providing flexibility refers to a comparison between a resin composition containing the compound according to the present invention and a resin composition not containing the compound according to the present invention. This means that the resin composition containing such a compound is more easily deformed and hardly broken.
  • Compound (1) can be colorless and transparent. Therefore, when compound (1) is blended with the resin composition, compound (1) is also prevented from causing coloring of the resin composition.
  • Compound (2) The compound according to the embodiment of the present invention is a compound represented by the following general formula (2) (sometimes abbreviated as “compound (2)”).
  • n 0 or 1.
  • Compound (2) can be used as an intermediate in the production of compound (1).
  • Compound (1) can be produced, for example, by the following method.
  • Compound (1) is not limited to those produced by the following method.
  • Compound (1) can be produced by subjecting a compound represented by the following general formula (3) (may be abbreviated as “compound (3)”) to epoxidation after hydroxylation.
  • compound (3) a compound represented by the following general formula (3) (may be abbreviated as “compound (3)”) to epoxidation after hydroxylation.
  • epoxidation means to introduce an epoxy ring or a group containing an epoxy ring, unless otherwise specified.
  • n 0 or 1.
  • the method for producing the compound (1) may include the following steps 1 and 2.
  • Step 1 a step of hydroxylating compound (3) to obtain compound (2).
  • Step 2 a step of epoxidizing the compound (2) obtained in the above step 1 to obtain a compound (1).
  • the method for producing compound (1) of the embodiment includes a step (step 1) of hydroxylating compound (3) to obtain compound (2). That is, the present invention provides a method for producing a compound (2), which comprises obtaining a compound (2) by hydroxylating the compound (3).
  • the method for producing the compound (1) of the embodiment may include a step of obtaining the compound (2) by hydroborating the compound (3) and then hydroxylating the compound (3).
  • the step 1 includes: The step of reacting the compound (3) with a hydroborating agent to form a hydroboron, followed by reacting with a peroxide to oxidize and hydroxylate to obtain the compound (2) may be performed.
  • n 0 or 1.
  • hydroborating agent a substance which reacts with an alkene to cause a hydroboration reaction can be used, and may be selected from various substances capable of hydroboration.
  • the hydroborating agent include compounds having a BH bond in the molecule, and examples thereof include borane, borane derivatives, and complexes thereof.
  • the borane derivative include a monoalkyl borane, a dialkyl borane and a compound represented by the following general formula (3a). From the viewpoint of yield and selectivity, 9-borabicyclo [3.3.1] nonane (9 —BBN) or NH 3 BH 3 [in the compound represented by the following general formula (3a), R 1 to R 6 are hydrogen atoms].
  • the complex examples include a tetrahydrofuran (THF) complex, a dimethylsulfide complex, and the like, and from the viewpoint of yield and selectivity, a 9-BBN.THF complex or an NH 3 BH 3 .THF complex is preferable.
  • THF tetrahydrofuran
  • dimethylsulfide complex examples include a dimethylsulfide complex, and the like, and from the viewpoint of yield and selectivity, a 9-BBN.THF complex or an NH 3 BH 3 .THF complex is preferable.
  • R 1 to R 6 are each independently a hydrogen atom or an alkyl group.
  • the alkyl group of R 1 to R 6 may be a linear or branched alkyl group having 1 to 4 carbon atoms.
  • Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.
  • Etc. can be exemplified.
  • Commercially available NH 3 BH 3 may be used, and a step of synthesizing NH 3 BH 3 may be provided prior to step 1.
  • Compound (3) can be obtained by multiplying isobutylene.
  • the compound (3) has an isomer that is a compound represented by the following general formula (3 ′) (may be abbreviated as “compound (3 ′)”).
  • the method for producing the compound (1) of the embodiment includes a step (step 1) of obtaining a compound (2) by hydroborating a raw material containing the compound (3) and the compound (3 ′) and then hydroxylating the raw material. May be something. Even if the raw material contains the compound (3 ′), the compound (3 ′) does not participate in the above reaction and can be removed after the reaction.
  • the amount of the hydroborating agent to be used may be appropriately adjusted according to the type of the compound in the reaction system, and the amount of the BH bond is 0.9 to 3 based on 1 equivalent of the carbon-carbon unsaturated bond to be reacted. It is preferably in the range of equivalents, more preferably in the range of 1 to 3 equivalents, and even more preferably in the range of 1.1 to 1.5 equivalents. When it is at least the lower limit, the yield will be better, and when it is at most the upper limit, purification will tend to be better.
  • the temperature (reaction temperature) of the reaction for hydroboration may be appropriately adjusted according to the type of the compound in the reaction system, but is preferably in the range of -80 to 120 ° C, for example, preferably in the range of -80 to 80 ° C.
  • the temperature is preferably in the range of -30 ° C, more preferably in the range of -30 to 50 ° C, and even more preferably in the range of -30 to 40 ° C.
  • it is preferably in the range of ⁇ 80 to 120 ° C., more preferably in the range of 0 to 100 ° C., and even more preferably in the range of 50 to 90 ° C.
  • the reaction rate is good and the reaction efficiency is good
  • the risk of decomposition of the raw materials and products tends to be reduced.
  • reaction time The time (reaction time) of the reaction for hydroboration may be appropriately adjusted according to other conditions such as the reaction temperature, and may be, for example, 0.5 to 100 hours.
  • the peroxide examples include hydrogen peroxide, perbenzoic acid, benzoyl peroxide and the like, and hydrogen peroxide is preferable.
  • Commercially available hydrogen peroxide can be used.
  • the amount of hydrogen peroxide to be used is not particularly limited, but is preferably in the range of 1 to 5 equivalents to 1 equivalent of the carbon-carbon unsaturated bond subjected to the reaction with the hydroborating agent, and preferably 1 to 2 equivalents. More preferably, it is within the range. When the amount is equal to or more than the lower limit, the reaction can proceed efficiently, and when the amount is equal to or less than the above upper limit, there is a tendency that a possibility that a side reaction such as oxidation of the generated hydroxy compound proceeds and the yield is reduced is reduced.
  • the oxidation in step 1 can be performed under basic conditions.
  • the basic condition includes a condition in which a peroxide is used in combination with a base, and includes a solution in which a peroxide and a base are added.
  • the base include inorganic bases.
  • the inorganic base include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, magnesium carbonate, and carbonate. Calcium, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate and the like can be mentioned.
  • sodium hydroxide, potassium hydroxide, or lithium hydroxide is preferred from the viewpoint of reaction yield, reaction temperature, simplicity of operation, economy, and the like.
  • reaction temperature may be appropriately adjusted depending on the type of the compound in the reaction system, but is preferably in the range of -80 to 80 ° C, for example, -30 to 50 ° C. Is more preferably in the range of ⁇ 30 to 40 ° C. When it is not less than the above lower limit, the reaction rate is good and the reaction efficiency is good, and when it is not more than the above upper limit, the risk of decomposition of the raw materials and products is small.
  • reaction time may be appropriately adjusted depending on other conditions such as the reaction temperature, and may be, for example, 0.5 to 100 hours.
  • the reaction of the above step 1 may be performed in the presence of a solvent.
  • a solvent One type of solvent may be used alone, or two or more types may be used in combination.
  • the solvent is not particularly limited, and examples thereof include n-hexane, pentane, cyclohexane, benzene, toluene, xylene, acetonitrile, acetone, ethyl acetate, diethyl ether, tetrahydrofuran, dimethyl sulfoxide, dimethyl sulfide, and trimethylamine. From above, diethyl ether, tetrahydrofuran, dimethyl sulfide, and trimethylamine are preferred, and diethyl ether and tetrahydrofuran are more preferred.
  • the method for producing compound (1) of the embodiment includes a step (step 2) of obtaining compound (1) by epoxidizing compound (2) obtained in step 1 above.
  • the method for producing the compound (1) of the embodiment includes a step of epoxidizing the compound (2) obtained in the step 1 and introducing an epoxy ring or a group containing an epoxy ring to obtain the compound (1). May be something.
  • the method for producing the compound (1) of the embodiment may include a step of glycidylating the compound (2) obtained in the above step 1 and introducing a glycidyl group to obtain the compound (1).
  • the step 2 includes: The step of reacting the compound (2) with epihalohydrin to perform epoxidation (glycidylation) to obtain the compound (1) may be performed.
  • n 0 or 1.
  • Epihalohydrin includes epichlorohydrin, epibromohydrin, ⁇ -methylepichlorohydrin and the like.
  • Epihalohydrin may be a compound represented by the following general formula (4) (sometimes abbreviated as “compound (4)”). These may be used alone or in combination of two or more.
  • halogen atom examples include a fluorine atom (-F), a chlorine atom (-Cl), a bromine atom (-Br), and an iodine atom (-I).
  • epichlorohydrin is preferred as epihalohydrin because of its easy industrial availability.
  • epihalohydrin used may be appropriately adjusted according to the type of the compound in the reaction system.
  • epihalohydrin may be added in the range of 2 to 10 equivalents to 1 equivalent of the hydroxyl group in compound (2). No.
  • the epoxidation reaction can be performed under basic conditions.
  • the basic conditions include in a liquid to which a basic catalyst has been added.
  • the basic catalyst include an alkaline earth metal hydroxide, an alkali metal carbonate, and an alkali metal hydroxide.
  • alkali metal hydroxides are preferred from the viewpoint of excellent epoxidation catalytic activity, and examples thereof include sodium hydroxide and potassium hydroxide.
  • these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass or in the form of a solid.
  • the amount of the basic catalyst to be used may be appropriately adjusted according to the type of the compound in the reaction system and the like. For example, 0.9 to 2 equivalents of the basic catalyst are added to 1 equivalent of the hydroxyl group in the compound (2). Are added at once or gradually added.
  • reaction temperature The temperature at which the compound (2) is reacted with epihalohydrin (reaction temperature) may be appropriately adjusted according to the type of the compound in the reaction system, and may be, for example, 20 to 120 ° C.
  • reaction time for reacting compound (2) with epihalohydrin may be appropriately adjusted according to other conditions such as the reaction temperature, and may be, for example, 0.5 to 10 hours.
  • the reaction in the above step 2 may be performed in the presence of a solvent.
  • a solvent One type of solvent may be used alone, or two or more types may be used in combination.
  • the solvent is not particularly limited, and examples thereof include n-hexane, pentane, cyclohexane, benzene, toluene, xylene, acetonitrile, acetone, ethyl acetate, diethyl ether, tetrahydrofuran, dimethyl sulfoxide, dimethyl sulfide, and trimethylamine.
  • Is preferably diethyl ether, tetrahydrofuran, dimethyl sulfide or trimethylamine, and more preferably diethyl ether or tetrahydrofuran.
  • the reaction product may be washed with water, and then unreacted epihalohydrin and an organic solvent used in combination may be distilled off under heating and reduced pressure conditions. Further, in order to further reduce the hydrolyzable halogen in the reaction product, the reaction product is dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, and methyl ethyl ketone, and alkali metal water such as sodium hydroxide and potassium hydroxide is used. The reaction can be further performed by adding an aqueous solution of an oxide. At this time, a phase transfer catalyst such as a quaternary ammonium salt or a crown ether may be present for the purpose of improving the reaction rate.
  • a phase transfer catalyst such as a quaternary ammonium salt or a crown ether may be present for the purpose of improving the reaction rate.
  • the amount thereof is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the reaction product.
  • the compound (1) can be suitably used as a reactive diluent for adding to a resin component to lower the viscosity of the resin component.
  • the reactive diluent according to the present invention is as follows.
  • a reactive diluent comprising the following component A, Component A: a compound represented by the following general formula (1). (In the formula (1), n is 0 or 1.)
  • the reactive diluent according to the present invention may be as follows.
  • a reactive diluent comprising the following component A, Component A: a compound represented by the above general formula (1).
  • the reactive diluent is preferably liquid at 25 ° C. and has a viscosity at 25 ° C. of 0.01 to 1000 mPa ⁇ s, 1 to 300 mPa ⁇ s, or 5 to 35 mPa ⁇ s. s or 5.5 to 10 mPa ⁇ s.
  • the viscosities are measured under the measurement conditions described in the examples or under compatible conditions to obtain the same results.
  • the compound represented by the general formula (1) is preferably liquid at 25 ° C., and has a viscosity at 25 ° C. of 0.01 to 1000 mPa ⁇ s, or 1 to 300 mPa ⁇ s.
  • the resin component is not particularly limited, but an epoxy resin before curing, such as a monomer or a prepolymer, is preferable.
  • composition according to the present invention is as follows.
  • Composition containing the following components A and B Component A: a compound represented by the following general formula (1), (In the formula (1), n is 0 or 1.)
  • Component B a compound having two or more groups containing an epoxy ring in the molecule.
  • composition according to the present invention containing the component A and the component B may further contain a curing agent (component C), if necessary.
  • the composition according to the present invention can further contain a curing accelerator (component D), a filler (component E), and the like, if necessary.
  • component D curing accelerator
  • component E filler
  • the component A is a compound represented by the general formula (1) (the compound (1)), and is the same as that described in the above ⁇ Compound (1) ⁇ , and thus description thereof will be omitted. .
  • Component B is a compound having two or more groups containing an epoxy ring (for example, an epoxy group or a glycidyl group) in a molecule.
  • the compound having two or more groups containing an epoxy ring in a molecule include a bifunctional or higher functional epoxy compound or an epoxy resin.
  • the compound having two or more groups containing an epoxy ring in the molecule may be a 2- to 10-functional epoxy compound, a 2- to 6-functional epoxy compound, or a 2- to 4-functional epoxy compound. Good.
  • the compound having two or more groups containing an epoxy ring in the molecule may be a bifunctional epoxy resin, a bifunctional epoxy resin, a bifunctional epoxy resin, or a bifunctional epoxy resin. Good.
  • a compound having two or more groups containing an epoxy ring in the molecule may be used as an epoxy resin by polymerizing and used as an epoxy compound or an epoxy resin having two or more groups containing an epoxy ring in the molecule.
  • bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol AD type epoxy resin; alicyclic epoxy resin; phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin And novolak type epoxy resins such as aralkyl novolak type epoxy resins; diglycidyl etherified products of polyfunctional phenols; and hydrogenated products thereof.
  • bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol AD type epoxy resin
  • alicyclic epoxy resin phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin
  • novolak type epoxy resins such as aralkyl novolak type epoxy resins; dig
  • the bifunctional or higher functional epoxy compound may be a bifunctional epoxy compound (compound having an epoxy ring-containing group having 2 to 10 in a molecule), a bifunctional hexafunctional epoxy compound, or a bifunctional epoxy compound. It may be a tetrafunctional epoxy compound.
  • a trifunctional or higher functional epoxy resin or a tetrafunctional or higher functional epoxy resin is preferable.
  • the bifunctional or higher functional epoxy resin may be a bifunctional epoxy resin (a compound having an epoxy ring-containing group of 2 to 10 in a molecule), a bifunctional hexafunctional epoxy resin, or a bifunctional epoxy resin. It may be a tetrafunctional epoxy resin.
  • a trifunctional epoxy compound or a tetrafunctional epoxy compound is preferably used as the compound having two or more groups containing an epoxy ring in the molecule.
  • a typical trifunctional epoxy compound that can be used in the present invention includes a compound having the following structural formula (product name: TEPIC (registered trademark)).
  • a typical tetrafunctional epoxy compound that can be used in the present invention includes a compound having the following structural formula (product name: jER (registered trademark) 1031S).
  • a typical other tetrafunctional epoxy compound that can be used in the present invention is a naphthalene-type epoxy compound having the following structural formula ((product name: EPICLON EXA-4700)).
  • the mixing ratio (A: B) of component A and component B may be 1 to 80:20 to 99, 5 to 70:30 to 95, and 20 to 60:40 on a weight basis. It may be 80.
  • the total blending ratio of component A and component B in the composition may be 1 to 99% by weight, or 5 to 80% by weight, when the total weight of the entire composition is 100% by weight. , From 10 to 60% by weight.
  • Examples of the curing agent (component C) include various curing agents used as curing agents for epoxy compounds and epoxy resins.
  • examples of the curing agent include phenol-based curing agents, amine-based curing agents, acid anhydrides, boron trifluoride monoethylamine, isocyanates, dicyandiamide, and urea resins.
  • the phenolic curing agent may be any monomer, oligomer, or polymer having two or more phenolic hydroxyl groups in one molecule, for example, a novolak phenol resin such as a phenol novolak resin or a cresol novolak resin; a naphthalene phenol Phenol resins such as resin, high ortho-type novolak phenol resin, terpene-modified phenol resin, terpene phenol-modified phenol resin, aralkyl-type phenol resin, dicyclopentadiene-type phenol resin, salicylaldehyde-type phenol resin, and benzaldehyde-type phenol resin.
  • a novolak phenol resin such as a phenol novolak resin or a cresol novolak resin
  • a naphthalene phenol Phenol resins such as resin, high ortho-type novolak phenol resin, terpene-modified phenol resin, terpene phenol
  • phenol novolak resins cresol novolak resins, and partially modified aminotriazine novolak resins are preferred.
  • the amine-based curing agent include aliphatic amines such as triethylenetetramine, tetraethylenepentamine and diethylaminopropylamine; and amine compounds such as aromatic amines such as metaphenylenediamine and 4,4'-diaminodiphenylmethane.
  • the acid anhydride include acid anhydrides such as phthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
  • curing agents may be used alone or in combination of two or more.
  • the amount of the curing agent used is preferably such that the ratio of the reactive group equivalent of the curing agent to the epoxy equivalent of component A and component B is 0.3 to 1.5 equivalents.
  • the compounding amount of the curing agent is within the above range, the control of the degree of curing is easy and the productivity tends to be good.
  • Examples of the curing accelerator (component D) include an imidazole compound, an organic phosphorus compound, a tertiary amine, and a quaternary ammonium salt.
  • the imidazole compound may be an imidazole compound having a potential by masking a secondary amino group of imidazole with acrylonitrile, isocyanate, melamine, acrylate, or the like.
  • imidazole compound used herein examples include imidazole, 2-methylimidazole, 4-ethyl-2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, and 2-heptadecylimidazole , 4,5-diphenylimidazole, 2-methylimidazoline, 2-ethyl-4-methylimidazoline, 2-undecylimidazoline, 2-phenyl-4-methylimidazoline and the like.
  • the compounding amount of the curing accelerator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the components A and B. If it is at least the above upper limit, a better curing promoting effect will be obtained, and if it is at most the above lower limit, the composition tends to be excellent in storage stability and physical properties of the cured product, and also economically.
  • Examples of the filler (component E) include oxides such as silica, aluminum oxide, zirconia, mullite, and magnesia; hydroxides such as aluminum hydroxide, magnesium hydroxide, and hydrotalcite; aluminum nitride, silicon nitride, boron nitride, and the like. Nitrides; natural minerals such as talc, montmorillonite and saponite; metal particles and carbon particles.
  • the average particle size of the inorganic filler is preferably 25 ⁇ m or less, more preferably 0.01 ⁇ m or more and 25 ⁇ m or less, further preferably 0.1 ⁇ m or more and 10 ⁇ m or less, and particularly preferably 0.3 ⁇ m or more and 7 ⁇ m or less.
  • the average particle size means a 50% volume cumulative diameter (D50) measured by a particle size distribution meter (laser diffraction scattering method).
  • the amount of the filler is preferably 5 to 90% by weight, more preferably 10 to 80% by weight, when the total weight of the whole composition is 100% by weight.
  • composition according to the present invention may further contain, if necessary, other components that do not correspond to the above components A to E.
  • Other components include other resins, solvents, additives, and the like.
  • Other resins include, for example, polyolefin, polyamide, polyimide and the like.
  • composition according to the present invention can be suitably used for the following applications.
  • the composition preferably contains the components A to C, and more preferably the components A to D.
  • the composition according to the present invention can be used as a sealing material for components such as semiconductor components.
  • the sealing material according to the present invention includes the composition according to the present invention.
  • As the sealing material for example, an aspect in which the space between the semiconductor component and the substrate, the periphery of the semiconductor component element is sealed with the sealing material, and an aspect in which the semiconductor component and the substrate are sealed with the sealing material (underfill ) Can be exemplified.
  • the sealing material is used as an underfill, for example, the gap between the substrate and the semiconductor component can be filled with the sealing material by the following procedure. First, a sealing material is applied to one end of a semiconductor component while heating the substrate to 70 to 130 ° C.
  • the gap between the substrate and the semiconductor component is filled with the sealing material by capillary action.
  • the substrate may be inclined, or a pressure difference may be generated between the inside and outside of the gap.
  • the gap can be sealed by heating and curing the sealing material.
  • the composition according to the present invention can be used as a substrate material.
  • a substrate can be manufactured by impregnating fibers such as glass fiber and carbon fiber with the composition according to the present invention, molding the resultant into a sheet, obtaining a prepreg, and heating and curing the prepreg. . Two or more prepregs may be stacked.
  • the cured product according to the present invention is a cured product of the composition according to the present invention.
  • the cured product according to the present invention can be obtained, for example, by heating and curing the composition according to the present invention at 80 to 200 ° C. for 0.2 to 6 hours.
  • the composition when the composition according to the present invention is a cured product, the composition preferably contains the components A to C, and more preferably the components A to D.
  • a substrate provided with a cured product of the composition according to the present invention can be provided.
  • the substrate is provided with a cured product of the composition according to the present invention, and as described below, a cured product of a prepreg, a cured product of a resin sheet, a copper-clad laminate, a printed circuit board, and a multilayer printed circuit board. It may have at least one selected from the group consisting of:
  • a prepreg including the composition and the fiber according to the present invention can be provided.
  • a resin sheet including the composition according to the present invention can be provided.
  • the resin sheet is obtained by molding the composition according to the present invention into a sheet, and the composition may be in a semi-cured state in order to enhance moldability.
  • the resin sheet is suitably used as an interlayer insulating material.
  • the substrate may be provided with a cured product of a prepreg having the composition and fibers according to the present invention. Two or more prepregs described above may be stacked.
  • the substrate can be manufactured, for example, by heat-curing and pressing the prepreg described above.
  • a copper-clad laminate in which a substrate and a copper foil are laminated can be provided.
  • the copper foil of the copper clad laminate can be processed to form a circuit. Therefore, as one embodiment of the present invention, a printed circuit board or a multilayer printed circuit board having a circuit formed on a board can be provided.
  • the printed circuit board or the multilayer printed circuit board may further include a cured product of the resin sheet.
  • a resin sheet may be provided instead of the substrate.
  • the copper-clad laminate can be manufactured by laminating the prepreg and the copper foil and forming the laminate under heat and pressure.
  • the heating and pressing conditions can be appropriately adjusted according to the thickness of the copper-clad laminate to be manufactured or the composition of the composition according to the present invention.
  • a printed circuit board or a multilayer printed circuit board can be manufactured by a conventional method such as a plating through-hole method or a build-up method, and can be obtained by laminating the above-mentioned prepreg or insulating resin sheet on an inner-layer wiring board and performing heat and pressure molding. Can be.
  • a printed circuit board or a multilayer printed circuit board can be manufactured by forming a circuit by etching a copper foil including a film.
  • the thickness of the prepreg, resin sheet, board, copper-clad laminate, printed circuit board, and multilayer printed circuit board is not particularly limited, but may be, for example, 0.1 to 10 mm, and may be, for example, 0.1 to 10 mm. It may be up to 5 mm.
  • the cured product of the composition containing the reactive diluent according to the present invention has moderate flexibility.
  • the cured product according to the present invention may have a flexural modulus value of 3000 MPa or less or 2500 MPa or less.
  • the lower limit of the flexural modulus is not particularly limited, the value of the flexural modulus may be 1500 MPa or more, or 2000 MPa or more.
  • the flexural modulus is assumed to be measured under the measurement conditions described in the examples or under compatible conditions that can provide the same result.
  • the cured product of the composition containing the reactive diluent according to the present invention has excellent dielectric properties.
  • the cured product according to the present invention may have a relative dielectric constant at 1 MHz or 1 GHz of 2 to 10, 2 to 5, or 3 to 4.
  • the relative dielectric constant is assumed to be measured under the measurement conditions described in the examples or under compatible conditions to obtain the same result.
  • the cured product according to the present invention may have a dielectric loss tangent at 1 MHz or 1 GHz of from 0.005 to 0.07, from 0.006 to 0.05, or from 0.007 to 0. 035 and may be 0.008 or more and less than 0.01. It is assumed that the dielectric loss tangent is measured under the measurement conditions described in the examples or under compatible conditions to obtain the same result.
  • the cured product having the above-mentioned dielectric properties may be read as a substrate, a copper-clad laminate, a printed circuit board, and a multilayer printed circuit board.
  • the cured product according to the present invention may have a water absorption value of 4% or less, 3% or less, or 1% or less.
  • the lower limit of the water absorption is not particularly limited, but may be 0.5% or more.
  • the fact that the water absorption is equal to or less than the above upper limit means that the cured product has excellent effect characteristics and that it has excellent water resistance or water repellency.
  • the water absorption is assumed to be measured under the measurement conditions described in the examples or under compatible conditions to obtain the same result.
  • an electronic component including the cured product according to the present invention can be provided. More specifically, an electronic component in which a component such as a semiconductor component and a substrate are sealed with a cured product of the sealing material according to the present invention can be provided.
  • the electronic component may use, for example, a sealing material as an underfill, the space between the component and the substrate may be sealed with a sealing material, or the space between the component and the substrate, and around the component. It may be sealed with a sealing material.
  • the components to be sealed include semiconductor elements, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, capacitors, and the like, but are not limited thereto.
  • the electronic component may include a terminal, a wire, a lead frame, other structures, and the like, in addition to the cured product of the substrate, the component, and the sealing material.
  • prepregs, resin sheets, substrates, copper-clad laminates, printed circuit boards, multilayer printed circuit boards, and electronic components can be manufactured from the composition according to the present invention. These have low dielectric properties, flexibility, and excellent heat resistance, and are used for mobile communication devices that handle high-frequency signals of 1 GHz or higher, base station devices, servers, electronic devices for networks such as routers, and large computers.
  • the present invention can be suitably used for components of printed circuit boards for networks used in various electronic devices.
  • reaction solution was ice-cooled again, and 79 ml (238 mmol) of 3M NaOHaq was added dropwise. Subsequently, a 30% by mass H 2 O 2 solution (80 ml) was added dropwise. After 17 hours, disappearance of the starting compound (3-1) was confirmed by GC. After separating the organic layer and the aqueous layer, K 2 CO 3 was added to the organic layer, and water remaining in the organic solvent was separated. After separating the aqueous layer, the same operation was further performed twice. The aqueous layers were combined and extracted three times with ethyl acetate. Finally, the organic layers were combined and dried over MgSO 4 .
  • the yield was 770 mg (3.18 mmol), the yield was 59.2%, the GC purity was 95.8%, the viscosity was 5.8 mPa ⁇ s (25 ° C.), and the epoxy equivalent was 242.
  • 1 H-NMR was used to confirm that the compound (1-1) was synthesized.
  • the E-type viscosity at 25 ° C. was measured using the following E-type viscometer.
  • Equipment used TV20 viscometer manufactured by Toki Sangyo Co., Ltd. Measurement temperature: 25 ° C
  • the measurement of the rotational viscosity of the compound was started with an E-type viscometer, and the numerical value of the rotational viscosity at the point where the indicated value of the rotational viscosity was stabilized was measured.
  • NH 3 BH 3 was synthesized.
  • the reagents used are as follows. ⁇ 7.57 g (200 mmol) of NaBH 4 ⁇ (NH 4) 2 SO 4 26.43g (200mmol) ⁇ THF 300ml ⁇ NH 3 (Liquid specific gravity about 0.6) 7.9g
  • a 5% (v / v) NH 3 / THF solution (200 ml) and a 1M NH 3 / THF solution (100 ml) were prepared by blowing ammonia gas into THF under ice cooling.
  • ⁇ Preparation 1 of composition> The following materials were blended at a blending ratio (parts by weight) shown in Table 1 to obtain a composition according to the present invention.
  • Epoxy resin phenol novolak type (liquid, epoxy equivalent 175 g / eq, viscosity 4500 Pa ⁇ s)
  • Epoxy resin II bisphenol A liquid type (manufactured by Nippon Steel & Sumitomo Metal, model number: YD-128, epoxy equivalent 190 g / eq, viscosity 11,000 mPa ⁇ s)
  • Curing agent Curing agent
  • Curing agent A 2-ethyl-4-methylimidazole (amine equivalent: 110 g / eq)
  • Curing agent B phenol novolak resin (PR-HF-6, manufactured by Sumitomo Bakelite Co.)
  • Curing agent C methyl hexahydroanhydride phthalate Acid (curing accelerator)
  • Curing accelerator A Triphenylphosphine (Hokuko TPP, manufactured by Hokuko Chemical Co., Ltd.)
  • the E-type viscosity at 25 ° C. was measured using the following E-type viscometer. Equipment used: Toki Sangyo Co., Ltd. TV20 viscometer Measurement temperature: 25 ° C About 1.2 mL of each resin composition prepared in the formulation example was placed in a cup attached to an E-type viscometer, and the cup was set to a temperature of 25 ° C. The measurement of the rotational viscosity of the compound was started with an E-type viscometer, and the numerical value of the rotational viscosity at the point where the indicated value of the rotational viscosity was stabilized was measured.
  • the tensile shear strength was measured under the following conditions. After degreasing a Cu plate (length 150 mm ⁇ width 25 mm ⁇ thickness 1.5 mm) and an Al plate (length 150 mm ⁇ width 25 mm ⁇ thickness 1.5 mm) with acetone, each of the resin compositions prepared in the formulation examples was prepared. A thin brush was applied, and the Cu plate and the Al plate were overlapped with an overlap distance of 12.5 mm. Then, it was fixed with scissors and cured at 100 ° C. for 1 hour and 180 ° C. for 5 hours to prepare a test piece. The test was started at a tensile speed of 5 mm / min, and the load when the test piece was broken was defined as the tensile shear bond strength.
  • Table 1 shows the evaluation results.
  • ⁇ Preparation 2 of composition> The following materials were blended at a blending ratio (parts by weight) shown in Table 2 to obtain a composition according to the present invention.
  • Table 2 shows the evaluation results.
  • ⁇ Preparation 3 of composition> The following materials were blended at a blending ratio (parts by weight) shown in Table 3 to obtain a composition according to the present invention.
  • PCT Measure absorption heat resistance evaluation
  • Table 3 shows the evaluation results.
  • the compound according to the present invention can be suitably used as a reactive diluent mixed with an epoxy resin.
  • the resin composition containing the compound according to the present invention has a reduced viscosity, and the cured product of the resin composition exhibits excellent dielectric properties, has good flexibility, and is externally applied with force. It has been found that it has an excellent property that it is hard to break even when it is broken.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Epoxy Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

Diluant réactif qui contient un composé représenté par la formule générale (1). (Dans la formule (1), n représente 0 ou 1.)
PCT/JP2019/019696 2018-07-17 2019-05-17 Diluant réactif, composition, matériau d'étanchéité, produit durci, substrat, composant électronique, composé époxy et procédé de production de composé WO2020017141A1 (fr)

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KR1020217000729A KR20210032383A (ko) 2018-07-17 2019-05-17 반응성 희석제, 조성물, 밀봉재, 경화물, 기판, 전자 부품, 에폭시 화합물, 및 화합물의 제조 방법
JP2020530910A JPWO2020017141A1 (ja) 2018-07-17 2019-05-17 反応性希釈剤、組成物、封止材、硬化物、基板、電子部品、エポキシ化合物、及び化合物の製造方法
CN201980047141.XA CN112424255A (zh) 2018-07-17 2019-05-17 反应性稀释剂、组合物、密封材、固化物、基板、电子部件、环氧化合物、及化合物的制造方法

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JP2000198830A (ja) * 1998-12-30 2000-07-18 Yuka Shell Epoxy Kk ポリカルボン酸組成物の製造方法
JP2004537598A (ja) * 2001-08-06 2004-12-16 ノバルティス アクチエンゲゼルシャフト 一定の置換ポリケチド、それらを含む医薬組成物および腫瘍処置におけるそれらの使用
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