CN112424255A - Reactive diluent, composition, sealing material, cured product, substrate, electronic component, epoxy compound, and method for producing compound - Google Patents
Reactive diluent, composition, sealing material, cured product, substrate, electronic component, epoxy compound, and method for producing compound Download PDFInfo
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- CN112424255A CN112424255A CN201980047141.XA CN201980047141A CN112424255A CN 112424255 A CN112424255 A CN 112424255A CN 201980047141 A CN201980047141 A CN 201980047141A CN 112424255 A CN112424255 A CN 112424255A
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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
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- 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
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- 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
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- 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
Abstract
A reactive diluent comprising a compound represented by the following general formula (1) (in the general formula (1), n is 0 or 1).
Description
Technical Field
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 for producing the epoxy compound, a method for producing the intermediate, and a method for producing the epoxy compound.
The present application claims priority based on applications published in japan on 7/17/2018, and applications 2018-134435 and 2018-134436, the contents of which are incorporated herein by reference.
Background
Epoxy resin compositions are widely used as interlayer insulating materials, sealing materials, base materials for various structural members, adhesive materials, and the like for printed circuit boards and the like of electric and electronic devices because of their excellent electrical properties and adhesive strength.
In particular, in current electronic devices, it is required to transmit and receive large amounts of information at high speed. However, as miniaturization of the wiring is advanced with the miniaturization of the device, the delay of transmission of an electric signal is increased due to a large inter-wiring capacity in the conventional interlayer insulating material, and transmission and reception of high-speed and large-capacity information are hindered.
Since the delay time is proportional to the inter-wiring capacity, if the inter-wiring capacity is reduced by reducing the dielectric constant of the interlayer insulating material, the transmission of electrical signals can be speeded up.
As the dielectric characteristics, 2 characteristics of the dielectric loss tangent and the relative permittivity are important. As a method for making an epoxy resin lower in dielectric properties, a method of increasing the amount of a silica filler is known. However, when the amount of the silica filler is increased, the dielectric loss tangent can be lowered, but there is a problem that the dielectric constant is increased.
Epoxy resin compositions are widely used in various applications because of their excellent adhesiveness and electromechanical properties. Epoxy resin compositions are generally added with various additives and the like to give preferable characteristics depending on the application. For example, when an epoxy resin composition is used as a semiconductor sealing material, it is necessary to fill a fine gap with the sealing material in accordance with the recent miniaturization of electronic devices, and thus a resin composition with a low viscosity is required. As a means for reducing the viscosity of the high-viscosity resin composition, a diluent is used. Diluents are divided into non-reactive diluents and reactive diluents. The reactive diluent reacts with the resin component of the resin composition and is cured together with the resin composition to become a part of a cured product, and therefore, there is an advantage that the diluent component is less likely to bleed out.
As a reactive diluent for reducing the viscosity of a resin composition to exhibit excellent dielectric characteristics, for example, a compound (trade name: FOLDI) in which a glycidyl group is bonded to an isostearic acid raw material via an ester bond as described in non-patent document 1 is disclosed.
Prior art documents
Non-patent document
Non-patent document 1: "low dielectric constant reactive diluent FOLDI" [ online ], japan, hei 28 years, 10 months, 5 days, [ hei 30 years, 6 months, 13 days search ], internet < URL: http:// www.nissanchem.co.jp/products/chemicals/pdf/FOLDI.pdf > (see description of FIGS.)
Disclosure of Invention
Problems to be solved by the invention
When the epoxy resin composition is formed into a cured product, the cured product becomes rigid due to its high elastic modulus, and thermal expansion or curing shrinkage occurs, and stress is easily applied to peripheral members. This causes a dimensional deviation or a crack to cause a malfunction. Therefore, a material having flexibility in forming a cured product is required.
The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a novel reactive diluent which can realize a reduction in viscosity of a resin composition, and can realize a low dielectric property and impart flexibility to a cured product of the resin composition.
It is also an object of the present invention to provide a composition comprising the aforementioned reactive diluent.
Further, an object of the present invention is to provide a sealing material comprising the composition.
Further, the present invention aims to provide a cured product of the composition.
Further, an object of the present invention is to provide a substrate comprising the cured product.
Further, an object of the present invention is to provide an electronic component comprising the cured product.
Further, an object of the present invention is to provide a novel epoxy compound which can realize a reduction in viscosity of a resin composition, and can realize low dielectricity and impart flexibility to a cured product of the resin composition.
Further, an object of the present invention is to provide an intermediate for producing the epoxy compound.
Further, the present invention aims to provide a method for producing the intermediate.
Further, the present invention aims to provide a method for producing the epoxy compound.
Means for solving the problems
[1] A reactive diluent comprising the following component A,
the component A is a compound represented by the following general formula (1).
(in the general formula (1), n is 0 or 1.)
[2] A composition comprising the following component A and component B,
the component A is a compound represented by the following general formula (1),
(in the general formula (1), n is 0 or 1.)
The component B is a compound having 2 or more epoxy ring-containing groups in the molecule.
[3] The composition according to [2], further comprising the following component C, wherein the component C is a curing agent.
[4] The composition according to [3], further comprising a component D which is a curing accelerator.
[5] A sealant comprising the composition according to [3] or [4 ].
[6] A cured product of the composition according to [3] or [4 ].
[7] A substrate comprising the cured product according to [6 ].
[8] An electronic component comprising the cured product according to [6 ].
[9] A compound represented by the following general formula (1).
(in the general formula (1), n is 0 or 1.)
[10] A compound represented by the following general formula (2).
(in the formula (2), n is 0 or 1.)
[11] A method for producing a compound represented by the following general formula (2), which comprises hydroxylating a compound represented by the following general formula (3) to obtain a compound represented by the following general formula (2).
(in the formula (3), n is 0 or 1.)
(in the formula (2), n is 0 or 1.)
[12] A method for producing a compound represented by the following general formula (1), which comprises epoxidizing a compound represented by the following general formula (2) to obtain a compound represented by the following general formula (1).
(in the formula (2), n is 0 or 1.)
(in the general formula (1), n is 0 or 1.)
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a novel reactive diluent capable of reducing the viscosity of a resin composition, and capable of realizing low dielectricity and imparting flexibility to a cured product of the resin composition can be provided.
In addition, according to the present invention, a composition comprising the aforementioned reactive diluent can be provided.
In addition, according to the present invention, a sealing material containing the composition can be provided.
Further, the present invention can provide a cured product of the composition.
Further, according to the present invention, a substrate provided with the cured product can be provided.
Further, according to the present invention, an electronic component provided with the cured product can be provided.
Further, the present invention can provide a novel epoxy compound which can realize a reduction in viscosity of a resin composition, and can realize low dielectricity and flexibility in a cured product of the resin composition.
Further, the present invention can provide an intermediate for producing the epoxy compound.
Further, the present invention can provide a method for producing the intermediate.
Further, the present invention can provide a method for producing the epoxy compound.
Detailed Description
Hereinafter, embodiments of the present invention will be described.
Compound (1)
The compound according to the embodiment of the present invention is a compound represented by the following general formula (1) (may be simply referred to as "compound (1)").
(in the general formula (1), n is 0 or 1.)
When the compound (1) is blended in a resin composition, the viscosity of the resin composition can be reduced, and low dielectric properties and flexibility can be imparted to a cured product of the resin composition.
The compound (1) has a saturated hydrocarbon structure in the molecule. Therefore, when blended in a resin composition, it is considered to contribute to the low dielectric properties of a cured product thereof.
The compound (1) has a branched saturated hydrocarbon structure in the molecule. Therefore, when blended in a resin composition, it is considered to contribute to a reduction in viscosity of the resin composition. Further, it is considered that this structure contributes to flexibility of a cured product when incorporated in a resin composition.
In the present specification, the term "imparting flexibility" means that a resin composition containing the compound of the present invention is easily deformed and hardly broken, compared with a resin composition not containing the compound of the present invention.
Further, the compound (1) may be colorless and transparent. Therefore, even when the compound (1) is blended in the resin composition, the compound (1) is 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) (may be simply referred to as "compound (2)").
(in the formula (2), n is 0 or 1).
The compound (2) is useful as an intermediate in the production of the compound (1).
Process for producing Compound (1) and Process for producing Compound (2)
The compound (1) can be produced, for example, by the following method. The compound (1) is not limited to the compound produced by the following method.
The compound (1) can be produced by hydroxylating a compound represented by the following general formula (3) (which may be simply referred to as "compound (3)") and then epoxidizing the hydroxylated compound.
In addition, in the present specification, the term "epoxidation" means, unless otherwise specified, introduction of an epoxy ring or a group containing an epoxy ring.
(in the formula (3), n is 0 or 1.)
The method for producing the compound (1) may include the following steps 1 to 2.
Step 1: a step of hydroxylating the compound (3) to obtain a compound (2).
And a step 2: a step of epoxidizing the compound (2) obtained in the step 1 to obtain a compound (1).
< working procedure 1 >
The method for producing the compound (1) of the embodiment includes a step (step 1) of obtaining a compound (2) by hydroxylating a compound (3).
Namely, a process for producing the compound (2) which comprises hydroxylating the compound (3) to obtain the compound (2).
The method for producing the compound (1) according to the embodiment may include a step of hydroborating the compound (3) and then hydroxylating the hydroborated compound to obtain the compound (2).
In the step 1, the compound (3) may be reacted with a hydroborating agent to hydroborate, and then reacted with a peroxide to oxidize and hydroxylate the compound to obtain the compound (2).
(wherein n is 0 or 1).
As the hydroborating agent, one which reacts with the alkene to cause hydroboration reaction can be usedThe substance may be selected from various substances capable of hydroboration. Examples of the hydroborating agent include compounds having a B — H bond in the molecule, and examples thereof include borane, borane derivatives, and complexes thereof. Examples of the borane derivative include monoalkylborane, dialkylborane, and a compound represented by the following general formula (3a), and 9-borabicyclo [3.3.1 ] is preferable from the viewpoint of yield and selectivity]Nonane (9-BBN) or NH3BH3[ in the compound represented by the following general formula (3a), R1～R6Is a hydrogen atom]. Examples of the complex include Tetrahydrofuran (THF) complex and dimethylsulfide complex, and 9-BBN THF complex or NH is preferable from the viewpoint of yield and selectivity3BH3THF complex.
(in the formula, R1～R6Each independently is a hydrogen atom or an alkyl group. )
R1～R6The alkyl group (C) 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 methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and the like.
NH3BH3Commercially available NH may be used, or NH may be synthesized by a method prior to the step 13BH3The process (2).
The compound (3) can be obtained by polymerizing isobutylene.
In addition, in the compound (3), although an isomer, which is a compound represented by the following general formula (3 ') (may be simply referred to as "compound (3 ')"), exists, as shown in examples described later, the compound (3) is more likely to react and be hydroxylated than the compound (3 ').
Therefore, the method for producing the compound (1) according to the embodiment may include a step (step 1) of hydroborating a raw material including the compound (3) and the compound (3') and then hydroxylating the hydroborated raw material to obtain the compound (2). Even if the starting material contains the compound (3 '), the compound (3') does not participate in the above reaction and can be removed after the reaction.
(in the formula (3'), m is 0 or 1.)
The amount of the hydroborating agent to be used may be appropriately adjusted depending on the kind of the compound in the reaction system, but the amount of the B-H bond is preferably in the range of 0.9 to 3 equivalents, more preferably in the range of 1 to 3 equivalents, and still more preferably in the range of 1.1 to 1.5 equivalents, relative to 1 equivalent of the carbon-carbon unsaturated bond to be reacted. When the content is not less than the lower limit, the yield is more favorable, and when the content is not more than the upper limit, the purification tends to be more favorable.
The temperature of the hydroboration reaction (reaction temperature) may be appropriately adjusted depending on the kind of the compound in the reaction system, but is preferably in the range of-80 to 120 ℃, more preferably in the range of-80 to 80 ℃, even more preferably in the range of-30 to 50 ℃, and even more preferably in the range of-30 to 40 ℃, as an example. Alternatively, the temperature is preferably in the range of-80 to 120 ℃, more preferably in the range of 0 to 100 ℃, and still more preferably in the range of 50 to 90 ℃.
When the amount is not less than the lower limit, the reaction rate is good and the reaction efficiency is good, and when the amount is not more than the upper limit, the possibility of decomposition of the raw material and the product tends to be low.
The time of the hydroboration reaction (reaction time) may be appropriately adjusted according to other conditions such as the reaction temperature, but may be, for example, 0.5 to 100 hours.
Examples of the peroxide include hydrogen peroxide, perbenzoic acid, and benzoyl peroxide, 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, and more preferably in the range of 1 to 2 equivalents, relative to 1 equivalent of carbon-carbon unsaturated bond to be reacted with the hydroboration agent. When the amount is not less than the lower limit, the reaction can be efficiently performed, and when the amount is not more than the upper limit, the possibility of the production yield being lowered due to the progress of side reactions such as oxidation of the produced hydroxy compound tends to be reduced.
The oxidation in step 1 may be carried out under alkaline conditions. The alkaline condition is a condition in which a peroxide and an alkali are used together, and a solution containing a peroxide and an alkali is used.
Examples of the base include inorganic bases, and examples of the inorganic base include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and lithium hydrogen carbonate. Among them, sodium hydroxide, potassium hydroxide, or lithium hydroxide is preferable from the viewpoints of reaction yield, reaction temperature, ease of operation, economy, and the like.
The temperature of the hydroxylation reaction (reaction temperature) may be appropriately adjusted depending on the kind of the compound in the reaction system, but is preferably in the range of-80 to 80 ℃, more preferably in the range of-30 to 50 ℃, and still more preferably in the range of-30 to 40 ℃ as an example. When the amount is not less than the lower limit, the reaction rate is good and the reaction efficiency is good, and when the amount is not more than the upper limit, the possibility of decomposition of the raw material and the product is low.
The time of the hydroxylation reaction (reaction time) may be appropriately adjusted according to other conditions such as the reaction temperature, but may be 0.5 to 100 hours, for example.
The reaction in step 1 may be carried out in the presence of a solvent. The solvent can be used alone in 1 kind, also can be combined with more than 2 kinds. 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, and from the viewpoint of yield, diethyl ether, tetrahydrofuran, dimethyl sulfide, and trimethylamine are preferable, and diethyl ether and tetrahydrofuran are more preferable.
< step 2 >
The method for producing the compound (1) according to the embodiment includes a step (step 2) of epoxidizing the compound (2) obtained in the step 1 to obtain the compound (1).
The method for producing the compound (1) according to the embodiment may include 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).
The method for producing the compound (1) according to the embodiment may include a step of glycidylating the compound (2) obtained in the step 1 and introducing a glycidyl group to obtain the compound (1).
The step 2 may be a step of obtaining the compound (1) by reacting the compound (2) with epihalohydrin to epoxidize (glycidate).
(wherein n is 0 or 1).
The epihalohydrin includes epichlorohydrin, epibromohydrin, β -methylepichlorohydrin, and the like. The epihalohydrin may be a compound represented by the following general formula (4) (may be simply referred to as "compound (4)"). They may be used alone or in combination of 2 or more.
(in the formula (4), X represents a halogen atom.)
Examples of the halogen atom include a fluorine atom (-F), a chlorine atom (-Cl), a bromine atom (-Br), and an iodine atom (-I).
Among these, epichlorohydrin is preferable from the viewpoint of easy industrial availability and the like.
The amount of epihalohydrin to be used may be appropriately adjusted according to the kind of compound in the reaction system, but for example, epihalohydrin may be added in an amount of 2 to 10 equivalents based on 1 equivalent of hydroxyl group in the compound (2).
The epoxidation reaction may be carried out under basic conditions. Under the alkaline condition, a solution to which a basic catalyst is added is exemplified.
Examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, from the viewpoint of excellent catalytic activity of epoxidation, alkali metal hydroxides are preferable, and examples thereof include sodium hydroxide and potassium hydroxide. When used, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or may be used in the form of a solid.
The amount of the basic catalyst to be used may be appropriately adjusted depending on the kind of the compound in the reaction system, and for example, 0.9 to 2 equivalents of the basic catalyst may be added together with or gradually added to 1 equivalent of the hydroxyl group in the compound (2).
The temperature (reaction temperature) for reacting the compound (2) with epihalohydrin may be appropriately adjusted according to the kind of the compound in the reaction system, but may be, for example, 20 to 120 ℃.
The time (reaction time) for reacting the compound (2) with epihalohydrin may be appropriately adjusted according to other conditions such as the reaction temperature, but may be 0.5 to 10 hours, for example.
The reaction of step 2 may be carried out in the presence of a solvent. The solvent can be used alone in 1 kind, also can be combined with more than 2 kinds. 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, and from the viewpoint of yield, diethyl ether, tetrahydrofuran, dimethyl sulfide, and trimethylamine are preferable, and diethyl ether and tetrahydrofuran are more preferable.
After the epoxidation reaction is completed, after the reaction product is washed with water, unreacted epihalohydrin and the organic solvent used in combination can be distilled off under heating and reduced pressure. In order to further reduce the hydrolyzable halogen in the reaction product, the reaction product may be dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, or methyl ethyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added to further carry out the reaction. In this case, a transfer catalyst such as a quaternary ammonium salt or a crown ether may be present for the purpose of increasing the reaction rate. The amount of the phase transfer catalyst used is preferably 0.1 to 3.0 parts by mass per 100 parts by mass of the reaction product. After the epoxidation reaction is completed, the formed salt is removed by filtration, washing with water, or the like, and the organic solvent is distilled off under heating and reduced pressure, whereby the compound (1) can be purified from the obtained reaction product.
Reactive diluents and compositions
The compound (1) can be added to a resin component and is suitably used as a reactive diluent for reducing the viscosity of the resin component.
That is, the reactive diluent according to the present invention is the following reactive diluent.
A reactive diluent comprising the following component a: a compound represented by the following general formula (1).
(in the general formula (1), n is 0 or 1).
The reactive diluent of the present invention may be the following reactive diluent.
A reactive diluent consisting of the following component a: a compound represented by the general formula (1).
The reactive diluent is preferably a liquid at 25 ℃ and has a viscosity of 0.01 to 1000 mPas, 1 to 300 mPas, 5 to 35 mPas, or 5.5 to 10 mPas at 25 ℃. The viscosity was measured under the measurement conditions described in examples, or under conditions compatible with the conditions described in examples, which gave the same results.
The compound represented by the general formula (1) is preferably a liquid at 25 ℃ and has a viscosity of 0.01 to 1000 mPas, 1 to 300 mPas, 5 to 35 mPas, or 5.5 to 10 mPas at 25 ℃. The viscosity was measured under the measurement conditions described in examples, or under conditions compatible with the conditions described in examples, which gave the same results.
The upper limit and the lower limit of the above-exemplified numerical range of the viscosity may be freely combined.
The resin component is not particularly limited, but is preferably an epoxy resin before curing, such as a monomer or a prepolymer.
Namely, the composition according to the present invention is the following composition.
A composition comprising the following component A and component B
Component A: a compound represented by the following general formula (1),
(in the general formula (1), n is 0 or 1).
Component B: a compound having 2 or more epoxy ring-containing groups in the molecule.
The composition of the present invention containing the component a and the component B may further contain a curing agent (component C) as required. The composition of the present invention may further contain a curing accelerator (component D), a filler (component E), and the like, as required. Hereinafter, each component will be described.
< ingredient A >)
The component A is the same as the compound represented by the general formula (1) (the compound (1)) described in the above-mentioned Compound (1), and therefore the description thereof is omitted here.
< ingredient B >
The component B is a compound having 2 or more epoxy ring-containing groups (for example, epoxy group and glycidyl group) in the molecule. Examples of the compound having 2 or more epoxy ring-containing groups in the molecule include 2-or more functional epoxy compounds and epoxy resins.
The compound having 2 or more epoxy ring-containing groups in the molecule may be a 2-10 functional epoxy compound, a 2-6 functional epoxy compound, or a 2-4 functional epoxy compound.
The compound having 2 or more epoxy ring-containing groups in the molecule may be a 2-10 functional epoxy resin, a 2-6 functional epoxy resin, or a 2-4 functional epoxy resin.
A compound having 2 or more epoxy ring-containing groups in the molecule may be used by polymerization, and the epoxy resin used is an epoxy resin, and examples of the epoxy compound or the epoxy resin having 2 or more epoxy ring-containing groups in the molecule include bisphenol epoxy resins such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin; an alicyclic epoxy resin; novolac type epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, and aralkyl novolac type epoxy resin; diglycidyl etherate of polyfunctional phenol; hydrides thereof, and the like. These epoxy resins may be used alone or in combination of 2 or more.
The epoxy compound having 2 or more functions is preferably an epoxy compound having 3 or more functions or an epoxy compound having 4 or more functions. The 2-or more-functional epoxy compound may be a 2-to 10-functional epoxy compound (a compound having 2-10 epoxy ring-containing groups in the molecule), may be a 2-to 6-functional epoxy compound, and may be a 2-to 4-functional epoxy compound.
The epoxy resin having 2 or more functions is preferably an epoxy resin having 3 or more functions or an epoxy resin having 4 or more functions. The 2-or higher-functional epoxy resin may be a 2-to 10-functional epoxy resin (a compound having 2-10 epoxy ring-containing groups in the molecule), a 2-to 6-functional epoxy resin, or a 2-to 4-functional epoxy resin.
The compound having 2 or more epoxy ring-containing groups in the molecule is preferably a 3-functional epoxy compound or a 4-functional epoxy compound.
Typical 3-functional epoxy compounds usable in the present invention include compounds having the following structural formula (product name: TEPIC (registered trademark)).
Typical examples of the 4-functional epoxy compound usable in the present invention include compounds having the following structural formula (product name: jER (registered trademark) 1031S).
Typical examples of the other 4-functional epoxy compound usable in the present invention include naphthalene type epoxy compounds having the following structural formula ((product name: EPICLON EXA-4700)).
The mixing ratio of the component A to the component B (A: B) can be 1-80: 20 to 99, and may be 5 to 70: 30-95, can be 20-60: 40-80.
The total amount of the component A and the component B in the composition may be 1 to 99% by weight, 5 to 80% by weight, or 10 to 60% by weight, based on 100% by weight of the total weight of the composition.
< ingredient C >
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 of monomers, oligomers, and polymers having 2 or more phenolic hydroxyl groups in 1 molecule, and examples thereof include novolak-type phenol resins such as phenol novolak resin and cresol novolak resin; phenol resins such as naphthalene-type phenol resin, high-ortho 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. Among them, preferred are phenol novolac resins, cresol novolac resins, and partially modified aminotriazine novolac resins.
Examples of the amine-based curing agent include aliphatic amines such as triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine; and amine compounds such as aromatic amines including m-phenylenediamine and 4, 4' -diaminodiphenylmethane.
Examples of the acid anhydride include acid anhydrides such as phthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
These curing agents may be used alone or in combination of 2 or more.
The amount of the curing agent used is preferably 0.3 to 1.5 equivalents of the equivalent ratio of the reactive group of the curing agent to 1 equivalent of the epoxy group of the component A and the component B. When the amount of the curing agent is within the above range, the degree of curing can be easily controlled, and productivity tends to be good.
< component D > examples of the curing accelerator (component D) include imidazole compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts and the like.
The imidazole compound may be an imidazole compound having a latent property obtained by masking a secondary amino group of imidazole with acrylonitrile, isocyanate, melamine, acrylate, or the like. Examples of the imidazole compound used herein include imidazole, 2-methylimidazole, 4-ethyl-2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 4, 5-diphenylimidazole, 2-methylimidazoline, 2-ethyl-4-methylimidazoline, 2-undecylimidazoline, and 2-phenyl-4-methylimidazoline.
In addition, a photoinitiator which generates radicals, anions or cations by photolysis and starts curing may be used.
These curing accelerators may be used alone or in combination of 2 or more.
The amount of the curing accelerator is preferably 0.01 to 20 parts by mass per 100 parts by mass of the component A and the component B. When the amount is not less than the upper limit, a more favorable curing accelerating effect is obtained, and when the amount is not more than the lower limit, the composition tends to have excellent storage stability and physical properties of a cured product, and to have excellent economical efficiency.
< ingredient E >
Examples of the filler (component E) include oxides such as silica, alumina, zirconia, mullite and magnesia; hydroxides such as aluminum hydroxide, magnesium hydroxide, and hydrotalcite; nitride ceramics such as aluminum nitride, silicon nitride, and boron nitride; natural minerals such as talc, montmorillonite and saponite; metal particles, carbon particles, and the like. The average particle diameter of the inorganic filler is preferably 25 μm or less, more preferably 0.01 μm or more and 25 μm or less, still more preferably 0.1 μm or more and 10 μm or less, and particularly preferably 0.3 μm or more and 7 μm or less. When the average particle diameter is not less than the lower limit, aggregation of the inorganic filler is easily suppressed, and the inorganic filler is easily dispersed in the resin. When the average particle diameter is not more than the upper limit, damage to the wire (wire) is easily suppressed during seal molding. The average particle diameter 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, based on 100% by weight of the total weight of the composition.
< other ingredients >
The composition of the present invention may further contain other components not corresponding to the components A to E as required. Examples of the other components include other resins, solvents, additives, and the like.
Examples of the other resin include polyolefin, polyamide, and polyimide.
Uses of the composition
The composition of the present invention can be suitably used for the following purposes. When the composition of the present invention is used by curing, the composition preferably contains the components a to C, more preferably the components a to D.
(sealing Material)
The composition of the present invention can be used as a sealing material for parts such as semiconductor parts.
The sealant of the present invention contains the composition of the present invention.
Examples of the sealing material include a form in which the periphery of the semiconductor component is sealed with the sealing material between the semiconductor component and the substrate, and a form in which the periphery of the semiconductor component is sealed with the sealing material between the semiconductor component and the substrate (underfill).
When the sealing material is used as the underfill, the gap between the substrate and the semiconductor component can be filled with the sealing material by, for example, the following steps. First, a sealing material is applied to one end of a semiconductor component while heating a substrate to 70 to 130 ℃. Then, the sealing material is filled in the gap between the substrate and the semiconductor member by capillary action. In this case, in order to shorten the time required for filling the sealing material, the substrate may be inclined, or a pressure difference may be generated between the inside and the outside of the gap. After the sealing material is filled in the gap, the gap can be sealed by heating and curing the sealing material.
(substrate Material)
The composition of the present invention can be used as a substrate material.
For example, a substrate can be produced by impregnating fibers such as glass fibers and carbon fibers with the composition of the present invention, molding the composition into a sheet to obtain a prepreg (preprg), and heating and curing the prepreg. The prepreg may be laminated in 2 or more sheets.
Curing products
The cured product of the present invention is a cured product of the composition of the present invention.
The cured product of the present invention can be obtained, for example, by heating the composition of the present invention at 80 to 200 ℃ for 0.2 to 6 hours to cure the composition by heating.
When the composition of the present invention is a cured product, the composition preferably contains the components a to C, and more preferably contains the components a to D.
In addition, as an embodiment of the present invention, a substrate comprising a cured product of the composition of the present invention can be provided.
The substrate is a substrate having a cured product of the composition of the present invention, and may be at least one selected from the group consisting of 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, as described later.
As an embodiment of the present invention, a prepreg provided with the composition and the fiber of the present invention can be provided.
In addition, as an embodiment of the present invention, a resin sheet comprising the composition of the present invention can be provided.
The resin sheet is obtained by molding the composition of the present invention into a sheet form, and the composition may be in a semi-cured state in order to improve moldability. The resin sheet is suitable as an interlayer insulating material.
The substrate may be a substrate having a cured product of a prepreg having the composition of the present invention and fibers. The prepreg may be laminated in 2 or more sheets.
The substrate can be produced by, for example, heating and pressing the prepreg.
In addition, as an embodiment of the present invention, there is provided a copper-clad laminate in which a substrate and a copper foil are laminated. The copper foil of the copper-clad laminate may be processed to form a circuit.
Therefore, as an embodiment of the present invention, a printed circuit board or a multilayer printed circuit board having a circuit formed on a substrate can be provided. The printed wiring board or multilayer printed wiring board may further comprise a cured product of the resin sheet. The resin sheet may be provided in place of the substrate.
The copper-clad laminate can be produced by laminating the prepreg and the copper foil and then heating and pressing the laminate. The heating and pressing conditions may be appropriately adjusted according to the thickness of the copper-clad laminate to be produced, the composition of the present invention, and the like.
The printed wiring board or multilayer printed wiring board can be produced by a conventional method such as a through-hole plating method or a build-up (build-up) method, and can be obtained by stacking the prepreg or insulating resin sheet described above on an inner layer wiring board and then heating and pressing the stack. For example, a printed circuit board or a multilayer printed circuit board can be manufactured by laminating copper foils on one or both surfaces of a prepreg of the present invention, heating and pressing the copper foils to produce a copper-clad laminate, then forming holes in the copper-clad laminate, plating through holes, and then etching the copper foil including the plating film to form a circuit.
The thickness of the prepreg, the resin sheet, the substrate, the copper-clad laminate, the printed circuit board, and the multilayer printed circuit board is not particularly limited, but may be, for example, 0.1 to 10mm, and may be 0.3 to 5 mm.
The cured product of the composition containing the reactive diluent of the present invention is a cured product to which appropriate flexibility is imparted. The cured product of the present invention may have a flexural modulus of 3000MPa or less, or 2500MPa or less. The lower limit of the flexural modulus is not particularly limited, but the flexural modulus may be 1500MPa or more, or 2000MPa or more. The flexural modulus was measured under the measurement conditions described in examples or under conditions compatible with the conditions that gave the same results.
The cured product of the composition containing the reactive diluent of the present invention is a cured product to which excellent dielectric characteristics are imparted.
The cured product of the present invention may have a relative dielectric constant value of 2 to 10, 2 to 5, or 3 to 4 at 1MHz or 1 GHz. The relative dielectric constant was measured under the measurement conditions described in examples, or under conditions compatible with the conditions that gave the same results.
The cured product of the present invention may have a dielectric loss tangent value of 0.005 to 0.07, 0.006 to 0.05, 0.007 to 0.035, or more than 0.008 and less than 0.01 at 1MHz or 1 GHz. The dielectric loss tangent was measured under the measurement conditions described in examples or under conditions compatible with each other under which the same results as those of the measurement conditions were obtained. Further, the cured product having the above dielectric properties may be referred to as a substrate, a copper-clad laminate, a printed circuit board, and a multilayer printed circuit board.
The water absorption of the cured product of the present invention may be 4% or less, 3% or less, or 1% or less. The lower limit of the water absorption rate is not particularly limited, but may be 0.5% or more. The water absorption of less than the upper limit means that the cured product has excellent advantageous properties and also means that the cured product has excellent water resistance and water repellency. The water absorption was measured under the measurement conditions described in examples, or under conditions compatible with each other, which gave the same results.
In addition, an electronic component including the cured product of the present invention can be provided as an embodiment of the present invention. More specifically, the present invention can provide an electronic component in which a substrate and a component such as a semiconductor component are sealed with a cured product of the sealing material of the present invention.
The electronic component may be sealed between the component and the substrate with a sealant, or between the component and the substrate and around the component with a sealant, for example, using a sealant as an underfill.
Here, examples of the member to be sealed include a semiconductor element, an integrated circuit, a large scale integrated circuit, a transistor, a semiconductor switching element, a diode, a capacitor, and the like, and are not limited thereto. The electronic component may include a terminal, a wire, a lead frame, another structure, and the like, in addition to the cured product of the substrate, the component, and the sealing material.
As described above, a prepreg, a resin sheet, a substrate, a copper-clad laminate, a printed circuit board, a multilayer printed circuit board, and an electronic component can be produced from the composition of the present invention. They have low dielectric properties, flexibility and excellent heat resistance, and can be suitably used for components of printed circuit boards for networks used in mobile communication devices operating high-frequency signals of 1GHz or higher, electronic devices for networks such as base station devices, servers and routers, and various electronic devices such as large computers.
While the embodiments of the present invention have been described above, the configurations and combinations thereof in the embodiments are examples, and combinations, additions, omissions, substitutions, and other changes of the configurations are possible within the scope not departing from the gist of the present invention. The present invention is not limited to the embodiments, but is limited only by the scope of the claims (claim).
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
< Synthesis of Compound >
[ Synthesis example 1]
In a 1L reaction vessel, 10g (59.4mmol) of a trimeric isobutylene raw material (manufactured by TCI) containing a compound represented by the following formula (3-1) (may be abbreviated as "compound (3-1)") and a compound represented by the following formula (3 '-1) (may be abbreviated as "compound (3' -1)") was added with dehydrated THF60ml under an argon flow and stirred. 9-BBN (89.1mmol) was added dropwise thereto at 10 ℃ or lower under cooling in an ice bath, and after 30 minutes, the temperature was raised to 35 ℃. After stirring overnight, the disappearance of the starting compound (3-1) was confirmed by Gas Chromatography (GC).
The reaction solution was cooled again in an ice bath, and 3M NaHAq 79ml (238mmol) was added dropwise. Then, 30 mass% of H was added dropwise2O2Solution (80 ml). After 17 hours, the disappearance of the starting compound (3-1) was confirmed by GC.
After separating the organic layer from the aqueous layer, K was added to the organic layer2CO3The water remaining in the organic solvent is separated. The aqueous layer was separated, and the same operation was performed 2 more times. The aqueous layers were combined and extracted 3 times with ethyl acetate. Finally, the organic layers were combined over MgSO4And (5) drying. After the drying agent was filtered, the solvent was distilled off under reduced pressure to obtain 18.22g of a crude colorless transparent oil. Further, unreacted internal olefin structure was removed at the time of distillation under reduced pressure.
The crude product was roughly purified by distillation under reduced pressure (bath temperature: 100 ℃, top temperature: 45 ℃, reduced pressure: 1.3kPa), and then purified by silica gel column (silica gel: 92.8g, eluent: heptane/ethyl acetate: 7/1) to obtain white solid OH. The yield was 2.74g (14.7mmol), the yield was 24.8%, and the GC purity was 99.9% or more. In addition, use1H-NMR confirmed that the compound represented by the following formula (2-1) (may be abbreviated as "Compound (2-1)").
The NMR data of the obtained compound (2-1) are shown below.
1H-NMR(300.40MHz，CDCl3Internal standard TMS)
0.92(s，18H)，1.15-1.41(d，4H)，1.57(m，lH)，3.53(d，2H)，7.28(s，OH)
[ Synthesis example 2]
Then, 1.0g (5.37mmol) of the compound (2-1) synthesized in Synthesis example 1, toluene, 73mg (0.215mmol) of tetrabutylammonium Hydrogen Sulfate (tetrabutylammonium Hydrogen Sulfate), and 50% NaHAq (5.4mL) were added to a 30mL reaction vessel, and the mixture was replaced with argon, followed by cooling in an ice bath and stirring. To this solution, 1.49g (16.1mmol) of epichlorohydrin was added dropwise, and the mixture was stirred for 30 minutes and warmed to room temperature. After 2 days, the disappearance of the starting compound (2-1-1) was confirmed by GC.
After quenching with water (queue), it was diluted with ethyl acetate. After separating the organic layer from the aqueous layer, the aqueous layer was extracted 3 times with ethyl acetate. Collect organic layers, wash 1 time with sat. NaClaq, Na2SO4And (5) drying. After the drying agent was filtered, the solvent was distilled off under reduced pressure to obtain 1.94g of a crude product as a pale yellow oil.
The crude product was purified by a Kugelrohr distillation apparatus (heating temperature: 160 to 240 ℃ C., reduced pressure: 0.1mmHg) to obtain a colorless, transparent and liquid compound represented by the following formula (1-1) (which may be referred to simply as "compound (1-1)") of the present invention. The yield was 770mg (3.18mmol), the yield was 59.2%, the GC purity was 95.8%, the viscosity was 5.8 mPas (25 ℃ C.), and the epoxy equivalent was 242. In addition, use1H-NMR confirmed the synthesis of the compound (1-1).
The following type E viscometer was used to measure the type E viscosity at 25 ℃.
The use equipment comprises the following steps: TV20 viscometer manufactured by Dongyi Kogyo K.K
Measuring temperature: 25 deg.C
About 1.2mL of the compound (1-1) was placed in a cup attached to an E-type viscometer, and the cup was set at a temperature of 25 ℃. The measurement of the rotational viscosity of the above-mentioned compound was started with an E-type viscometer, and the value of the rotational viscosity at the point where the indicated value of the rotational viscosity was stabilized was measured.
NMR data of the obtained compound (1-1) are shown below.
1H-NMR(300.40MHz，CDCl3Internal standard TMS)
0.92(s，18H)，1.15-1.36(d，4H)，1.74(m，1H)，2.61-2.77(d，2H)，3.14(m，1H)，3.40-3.67(d，18H)，3.38(t，2H).
[ Synthesis example 3]
A compound represented by the following formula (2-2) (which may be abbreviated as "compound (2-2)") was synthesized in the same manner as in Synthesis example 1 except that a tetraisobutylene raw material (manufactured by TCI) containing a compound represented by the following formula (3-2) (which may be abbreviated as "compound (3-2)") and a compound represented by the following formula (3 '-2) (which may be abbreviated as "compound (3' -2)") was used instead of the triisobutene raw material.
NMR data of the obtained compound (2-2) are shown below.
1H-NMR(300.40MHz，CDCl3Internal standard TMS)
0.87(s，6H)，0.92(s，9H)，0.97(s，9H)，1.02(d，2H)，1.17-1.41(d，4H)，1.60(m，1H)，3.50(m，2H)，7.21(s，0H).
[ Synthesis example 4]
A reaction was carried out in the same manner as in Synthesis example 2 except for using the compound (2-2) obtained above in place of the compound (2-1) to obtain a colorless, transparent and liquid compound represented by the following formula (1-2) of the present invention (which may be simply referred to as "compound (1-2)"). The total yield of the compound (1-2) was 17.2%, GC purity was 98.2%, and viscosity was 33 mPas (g/g)25 ℃ C.), epoxy equivalent of 298. In addition, use1H-NMR confirmed that Compound (1-2) was synthesized. The viscosity of the compound (1-2) was measured in the same manner as in Synthesis example 2.
The NMR data of the obtained compound (1-2) are shown below.
1H-NMR(300.40MHz，CDCl3Internal standard TMS)
0.87(s，6H)，0.92(s，9H)，0.97(s，9H)，1.02(d，2H)，1.15-1.36(d，4H)，1.74(m，1H)，2.64-2.79(d，2H)，3.17(m，1H)，3.42-3.69(d，2H)，3.36(t，2H).
[ Synthesis example 5]
Except that NH is used instead of the aforementioned 9-BBN3BH3The reaction was carried out in the same manner as in Synthesis example 1 to synthesize the above-mentioned compound (2-1). The details are described below.
(NH3BH3Synthesis)
First, NH is synthesized3BH3. The reagents used were as follows.
As a preliminary preparation, 5% (v/v) NH was prepared by blowing ammonia gas into THF under cooling in an ice bath3THF solution (200ml) and 1M NH3THF solution (100 ml).
A500 ml flask was charged with chilled 5% (v/v) NH at atmospheric pressure3THF solution (200 ml). Sodium borohydride and ammonium sulfate were added thereto under cooling in an ice bath, and the mixture was stirred at 0 ℃ for 2 hours and then at room temperature for 8 hours.
To the resulting white suspension, 1M NH was added3THF solution (100ml) was stirred for 30 minutes, then filtered through a celite pad and washed with THF. Concentrating the filtrate, and drying under reduced pressure at room temperature to obtainTo 4.73g NH as a white solid3BH3(yield: 76.6%, no impurity peak). Use of1B-NMR was confirmed to synthesize NH3BH3。
In a 200mL reaction vessel, THF25mL was dehydrated and NH was added under atmospheric pressure3BH31.16g (37.43mmol) of triisobutene starting material (TCI Co., Ltd.) containing the compound (3-1) and the compound (3' -1) was added to 25.20g (149.7mmol) of triisobutene starting material (TCI Co., Ltd.) and stirred, and after 1 hour of reaction under reflux heating at 78 ℃ and 10ml of THF was distilled off from the reaction solution, after 2 hours of reaction under reflux heating at 80 ℃ the disappearance of the starting compound (3-1) was confirmed by Gas Chromatography (GC).
To the reaction mixture, 17ml (49.9mmol) of 3M NaHAq was added, and the mixture was refluxed at 73 ℃ for 3 hours. After cooling to 30 ℃ this was added dropwise with 30 mass% H over 10 minutes2O2Solution 17ml (154.2 mmol). After warming to 45 ℃ the mixture was stirred at room temperature overnight.
The resulting product was purified in the same manner as in Synthesis example 1 to obtain a white solid OH compound. The yield was 6.7g, the yield was 24.0%, and the GC purity was 99.0% or more. In addition, use1H-NMR confirmed the synthesis of the compound (2-1).
< preparation of composition 1 >
The following materials were blended in the blending ratios (parts by weight) shown in table 1 to obtain the composition of the present invention.
(reactive diluent)
Compound (1-1)
Compound (1-2)
(epoxy resin)
Epoxy resin I: phenol novolak type (liquid, epoxy equivalent 175g/eq, viscosity 4500Pa · s)
Epoxy resin II: bisphenol A liquid type (made by Nippon Steel Co., Ltd., type: YD-128, epoxy equivalent 190g/eq, viscosity 11,000 mPa. s)
(curing agent)
Curing agent a: 2-ethyl-4-methylimidazole (amine equivalent 110 g/eq.) curing agent B: phenol novolac resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-HF-6), curing agent C: methylhexahydrophthalic anhydride
(curing accelerators)
Curing accelerator a: triphenylphosphine (manufactured by Beixing chemical industry Co., Ltd., ホクコー TPP), curing accelerator B: 2-ethyl-4-methylimidazole
(Filler)
Filler a: silicon dioxide powder
Filler B: boron nitride powder
< evaluation >
(viscosity)
The following type E viscometer was used to measure the type E viscosity at 25 ℃.
The use equipment comprises the following steps: TV20 viscometer manufactured by Dongyi Kogyo K.K
Measuring temperature: 25 deg.C
About 1.2mL of each resin composition adjusted in the compounding examples was placed in a cup attached to an E-type viscometer, and the cup was set at a temperature of 25 ℃. The measurement of the rotational viscosity of the above-mentioned compound was started with an E-type viscometer, and the value of the rotational viscosity at the point where the indicated value of the rotational viscosity was stabilized was measured.
(tensile shear bond Strength)
The tensile shear bond strength was measured under the following conditions.
After degreasing a Cu plate (length 150 mm. times. width 25 mm. times. thickness 1.5mm) and an Al plate (length 150 mm. times. width 25 mm. times. thickness 1.5mm) with acetone, each of the resin compositions adjusted in the formulation examples was thinly applied with bristles, and the Cu plate and the Al plate were stacked at an overlapping distance of 12.5 mm. Then, the resultant was fixed with a jig and cured at 100 ℃ for 1 hour and 180 ℃ for 5 hours to prepare a test piece. The test was started at a tensile rate of 5mm/min, and the load at the time of breaking the test piece was defined as the tensile shear adhesion strength.
The evaluation results are shown in table 1.
TABLE 1
< preparation of composition 2 >
The following materials were blended in the blending ratios (parts by weight) shown in table 2 to obtain the composition of the present invention.
(reactive diluent)
Compound (1-1)
(epoxy Compound 1)
TEPIC-S (manufactured by Nissan chemical industries, Ltd., epoxy equivalent 100)
(epoxy Compound 2)
JeR1031S (made by Mitsubishi chemical Co., Ltd., epoxy equivalent 196)
(curing agent)
MH-700(MeHHPA, New Ri Nature chemical Co., Ltd., acid anhydride equivalent 164)
(curing accelerators)
Curezol (2E4MZ, product of Sizhou Kaisha)
< evaluation >
(preparation of test piece)
The materials of the reactive diluent, epoxy compound and curing agent were mixed in a predetermined formulation shown in table 2. Next, a curing accelerator was added and mixed in a predetermined formulation shown in table 2, and the mixture was poured into a cavity for injection molding. The injection molding chamber was placed in a hot air circulation type oven, heated at 100 ℃ for 2 hours, and then cured at 150 ℃ for 5 hours to obtain a test piece.
(bending test)
The bending test was performed under the following conditions.
Test methods: according to JIS K7171
Measurement items: strength and modulus of elasticity
Test piece shape: 65mm by 25mm by 3mm
Measurement conditions: testing speed; 1.5mm/min
Distance between fulcrums: 48mm
Measurement number: n is 3
Test environment: 23 ℃ plus or minus 1 ℃ and 50% RH plus or minus 5% RH
The measurement device: universal material tester 5582 type (INSTRON corporation)
(relative permittivity, dielectric loss tangent)
The relative dielectric constant and the dielectric loss tangent were measured under the following conditions.
Test methods: measurement items according to IEC 60250 (automatic balance bridge method): relative dielectric constant and dielectric loss tangent
Test piece shape: 60mm × 60mm × 3mm
Measurement conditions: frequency; 1MHz
Measurement temperature: 23 deg.C
Electrode size: diameter of main electrode
Inner diameter of ring electrode
Electrode material: conductive silver paint
Measurement number: n is 2(1 measurement 2 times)
State regulation: 23 ℃ plus or minus 2 ℃, 50% RH plus or minus 5% RH, 48 hours test environment: 23 ℃ plus or minus 2 ℃ and 50% RH plus or minus 5% RH
The measurement device: precision LCR meter E4980A (Agilent Technology Co., Ltd.)
(Water absorption)
The water absorption was measured under the following conditions.
Test piece shape: about 30mm by 40mm by 3mm
Pretreatment: 50 ℃, 24 hours (hot air circulation oven) test conditions: boiling water (100 deg.C), 100 hours
Measurement number: n is 2
The evaluation results are shown in table 2.
TABLE 2
About 1 analytical value of flexural modulus … by the tangent method
2 is not broken
< preparation of composition 3 >
The following materials were blended in the blending ratios (parts by weight) shown in Table 3 to obtain the compositions of the present invention.
(reactive diluent)
Compound (1-1)
Compound (1-2)
(epoxy compound)
TEPIC-S (manufactured by Nissan chemical industries, Ltd., epoxy equivalent 100)
(curing agent)
MH-700(MeHHPA, New Ri Nature chemical Co., Ltd., acid anhydride equivalent 164)
(curing accelerators)
Curezol (2E4MZ, product of Sizhou Kaisha)
(Filler)
Silica powder (average particle diameter 25 μm)
< manufacture of prepreg and printed wiring board >
Each resin composition prepared according to the formulation shown in table 3 was impregnated into glass fibers, and then dried at 165 ℃ for 3 to 10 minutes to prepare prepregs. The prepreg 2 layers (ply) were laminated with a copper foil having a thickness of 18 μm, and then pressed to obtain a laminated sheet having a thickness of 0.2 mm.
< evaluation >
(copper foil adhesion (peel Strength: P/S))
According to the evaluation criteria of IPC-TM-6502.4.8, the laminated sheet was impregnated with a copper etching solution to remove the copper foil, the circuit pattern (copper foil) formed on the obtained printed circuit board was pulled up in the direction of 90 degrees, and the peeling time point of the circuit pattern was measured to perform evaluation (kgf/cm).
(evaluation of moisture absorption Heat resistance (PCT))
The above-mentioned printed circuit board was left to stand for 4 hours to 121 ℃ and 0.2MPa using a pressure cooker test apparatus (ESPEC, EHS-411MD), and then the printed circuit board was immersed in molten solder at 288 ℃ for 10 seconds, and the time until the peeling phenomenon occurred between the insulating layer and the copper foil, between the insulating layer and the metal core, or between the insulating layers was measured and evaluated.
The product is qualified after more than 2 hours.
(relative permittivity and dielectric loss tangent)
The printed circuit board was measured for the relative permittivity and the dielectric loss tangent at a frequency of 1GHz by a relative permittivity measuring apparatus (RF impedance/Material Analyzer, Agilent).
The evaluation results are shown in table 3.
TABLE 3
From the results shown above, it is understood that the compound of the present invention can be suitably used as a reactive diluent to be mixed with an epoxy resin. The resin composition containing the compound of the present invention has a reduced viscosity, and a cured product of the resin composition has the following excellent properties: exhibits excellent dielectric characteristics, has good flexibility, and is less likely to break even when applied with an external force.
Claims (12)
1. A reactive diluent comprising the following component A,
the component A is a compound represented by the following general formula (1),
in the general formula (1), n is 0 or 1.
2. A composition comprising the following component A and component B,
the component A is a compound represented by the following general formula (1),
in the general formula (1), n is 0 or 1;
the component B is a compound having 2 or more epoxy ring-containing groups in the molecule.
3. The composition of claim 2, further comprising component C, which is a curing agent.
4. The composition of claim 3, further comprising component D, which is a cure accelerator.
5. A sealant comprising the composition according to claim 3 or 4.
6. A cured product of the composition according to claim 3 or 4.
7. A substrate comprising the cured product according to claim 6.
8. An electronic component comprising the cured product according to claim 6.
9. A compound represented by the following general formula (1),
in the general formula (1), n is 0 or 1.
10. A compound represented by the following general formula (2),
in the formula (2), n is 0 or 1.
11. A method for producing a compound represented by the following general formula (2), which comprises subjecting a compound represented by the following general formula (3) to hydroxylation to obtain a compound represented by the following general formula (2),
in the formula (3), n is 0 or 1;
in the formula (2), n is 0 or 1.
12. A method for producing a compound represented by the following general formula (1), which comprises epoxidizing a compound represented by the following general formula (2) to obtain a compound represented by the following general formula (1),
in the formula (2), n is 0 or 1;
in the general formula (1), n is 0 or 1.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP2018134436 | 2018-07-17 | ||
| JP2018134435 | 2018-07-17 | ||
| JP2018-134436 | 2018-07-17 | ||
| JP2018-134435 | 2018-07-17 | ||
| PCT/JP2019/019696 WO2020017141A1 (en) | 2018-07-17 | 2019-05-17 | Reactive diluent, composition, sealing material, cured product, substrate, electronic component, epoxy compound and method for producing compound |
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| Publication Number | Publication Date |
|---|---|
| CN112424255A true CN112424255A (en) | 2021-02-26 |
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| Country | Link |
|---|---|
| JP (1) | JPWO2020017141A1 (en) |
| KR (1) | KR20210032383A (en) |
| CN (1) | CN112424255A (en) |
| TW (1) | TW202006038A (en) |
| WO (1) | WO2020017141A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7241389B2 (en) * | 2019-02-21 | 2023-03-17 | ナミックス株式会社 | Liquid epoxy resin composition and cured product obtained by curing it |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4924026A (en) * | 1989-08-11 | 1990-05-08 | International Flavors & Fragrances Inc. | Triisobutylene alcohols and esters, uses thereof in perfumery and halogenated intermediates useful for preparing same |
| US6235931B1 (en) * | 1998-12-30 | 2001-05-22 | Shell Oil Company | Partial oxidation of polyoxyalkylene polyol compositions to polycarboxylic acid compositions |
| US20030087934A1 (en) * | 2001-08-06 | 2003-05-08 | Kinder Frederick R. | Certain substituted polyketides, pharmaceutical compositions containing them and their use in treating tumors |
| JP2012102230A (en) * | 2010-11-10 | 2012-05-31 | Honda Motor Co Ltd | Curable resin composition and electric and electronic part using the same |
| US20160340305A1 (en) * | 2014-01-03 | 2016-11-24 | Daniel Halsell ESS | Direct stereospecific synthesis of unprotected aziridines from olefins |
-
2019
- 2019-05-17 TW TW108117159A patent/TW202006038A/en unknown
- 2019-05-17 WO PCT/JP2019/019696 patent/WO2020017141A1/en active Application Filing
- 2019-05-17 KR KR1020217000729A patent/KR20210032383A/en not_active Application Discontinuation
- 2019-05-17 JP JP2020530910A patent/JPWO2020017141A1/en active Pending
- 2019-05-17 CN CN201980047141.XA patent/CN112424255A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4924026A (en) * | 1989-08-11 | 1990-05-08 | International Flavors & Fragrances Inc. | Triisobutylene alcohols and esters, uses thereof in perfumery and halogenated intermediates useful for preparing same |
| US6235931B1 (en) * | 1998-12-30 | 2001-05-22 | Shell Oil Company | Partial oxidation of polyoxyalkylene polyol compositions to polycarboxylic acid compositions |
| US20030087934A1 (en) * | 2001-08-06 | 2003-05-08 | Kinder Frederick R. | Certain substituted polyketides, pharmaceutical compositions containing them and their use in treating tumors |
| JP2012102230A (en) * | 2010-11-10 | 2012-05-31 | Honda Motor Co Ltd | Curable resin composition and electric and electronic part using the same |
| US20160340305A1 (en) * | 2014-01-03 | 2016-11-24 | Daniel Halsell ESS | Direct stereospecific synthesis of unprotected aziridines from olefins |
Non-Patent Citations (5)
| Title |
|---|
| CRANDALL，J. K. ET AL.: "Reactions of Ketenes with Peracids and Ozone", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
| WHITMORE，F.C. ET AL.: "Grignard Reductions. IX. Further Studies on the Reduction of Acid Halides", 《JOURNAL OF AMERICAN CHEMICAL SOCIETY》 * |
| 刘尚乐等: "《环氧胶黏剂》", 30 November 1978, 山西人民出版社 * |
| 唐除痴等: "《不对称反应概论》", 31 October 2017, 南开大学出版社 * |
| 许长清: "《合成树脂及塑料手册》", 30 November 1991, 化学工业出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2020017141A1 (en) | 2021-09-24 |
| KR20210032383A (en) | 2021-03-24 |
| TW202006038A (en) | 2020-02-01 |
| WO2020017141A1 (en) | 2020-01-23 |
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