CN107868230B - Curing agent for epoxy resin and preparation method thereof - Google Patents

Curing agent for epoxy resin and preparation method thereof Download PDF

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CN107868230B
CN107868230B CN201710854908.2A CN201710854908A CN107868230B CN 107868230 B CN107868230 B CN 107868230B CN 201710854908 A CN201710854908 A CN 201710854908A CN 107868230 B CN107868230 B CN 107868230B
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李垠龙
李智爱
郑榕洙
李贵恒
黄载锡
白美贞
郑源浩
崔湖京
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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
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/625—Hydroxyacids
    • C08G59/628—Phenolcarboxylic acids
    • 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
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
    • C08G59/4276—Polyesters
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    • 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
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/133—Hydroxy compounds containing aromatic rings
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/105—Esters; Ether-esters of monocarboxylic acids with phenols
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

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Abstract

The present invention relates to a curing agent for epoxy resins, and more particularly, to a curing agent for epoxy resins, which can be widely used in the field of electric and electronic devices, since a cured product of the curing agent has a high glass transition temperature, a low moisture absorption, an excellent adhesive force, a high peel strength, and a low thermal expansion coefficient, and also has significantly improved electrical characteristics such as dielectric constant and dielectric loss.

Description

Curing agent for epoxy resin and preparation method thereof
Technical Field
The present invention relates to a curing agent for epoxy resins and a method for preparing the same, and more particularly, to a curing agent for epoxy resins, wherein a cured product of the curing agent has high glass transition temperature, low moisture absorption, excellent adhesive force, high peel strength, and low thermal expansion coefficient, and remarkably improves electrical properties such as dielectric constant and dielectric loss.
Background
Recently, with the increase in capacity and speed of the semiconductor industry, the trend toward miniaturization and miniaturization has been progressing through the integration of dissimilar metals and components. In such a fusion-compositing technology, a packaging technology for inserting a different material and a component into a device is a core, and therefore, it is necessary to develop a core material having a Low coefficient of thermal expansion (Low CTE), a Low dielectric constant (Low Dk), a Low dielectric loss (LowDf), and heat resistance.
In a next-generation Integrated Circuit (IC) substrate (substrate), a Printed Circuit Board (PCB), a Flexible display substrate (Flexible display substrate), and the like, as a method for achieving high integration, high miniaturization, and high performance, an integration level of a semiconductor device for processing a large capacity in a short time is generally increased, which means that a gap between a width of a biological wiring of the device and a width is narrowed, and the high speed of the device can be achieved by increasing a switching speed of a transistor.
As described above, various methods for reducing the wiring width of the device have been recently disclosed, but there is a limitation in reducing the circuit pattern pitch in the conventional patterning by copper etching in order to form a fine circuit pattern. Thus, Copper (Copper) circuit pattern formation by a chemical method can be achieved to 20/20 μmm or less, but there is a disadvantage that adhesion is significantly reduced due to surface illuminance of a pattern not formed. Thus, in order to realize a high-density chip that achieves a narrow line width between wirings on the high-density chip, a polymer substance having a low dielectric constant and a low dielectric loss, which is excellent in electrical insulation properties, and also excellent in adhesion is required.
As a polymer substance having the above-described effects and which is often used, an epoxy (epoxy) resin having excellent electrical characteristics, mechanical characteristics, and adhesion is widely used, and as a curing agent, a curing agent having active hydrogen such as an amine (amine) compound and a phenol (phenol) compound is often used.
However, when an epoxy resin is cured as a curing agent having such active hydrogen, there are problems that a polar high hydroxyl group is generated by a reaction between an epoxy group and active hydrogen, so that the moisture absorption property of a final cured product is increased, and electrical properties such as a dielectric constant and a dielectric loss are reduced, and that the glass transition temperature of the cured product is low, so that heat resistance is reduced, and mechanical properties are reduced, so that the above-mentioned properties cannot be satisfied at the same time.
Further, even if one of the physical properties of the final cured product is good, the other is also deteriorated, and particularly, as the electric characteristics such as dielectric constant and dielectric loss are deteriorated, there is a problem that low hygroscopicity, high heat resistance, excellent mechanical characteristics and excellent electric characteristics cannot be satisfied at the same time.
Korean patent application No. 2011-0105763 discloses an epoxy resin composition that can be usefully used as an adhesive and sealing material for electronic devices, but in the case of a curing agent contained in the above composition, it is impossible to minimize dielectric constant and dielectric loss by using a general amine-based curing agent, and there is a problem that the cured product has high hygroscopicity and adhesion cannot be increased, and thus it is impossible to use the cured product as a high-performance and high-integration electrical and electronic material.
Documents of the prior art
Patent document
Granted patent publications: 2011-0105763
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a curing agent for epoxy resins, which enables a cured product to have a high glass transition temperature, a low moisture absorption, an excellent adhesive force, a high peel strength, a low thermal expansion coefficient, and significantly improved electrical characteristics such as a dielectric constant and a dielectric loss.
The second problem to be solved by the present invention is to provide a sealing material for electric and electronic devices or a laminate material for electric and electronic substrates, which has high glass transition temperature, low moisture absorption, excellent adhesion, high peel strength and low thermal expansion coefficient, and which has significantly improved electrical characteristics such as dielectric constant and dielectric loss.
The present invention has been made in view of the above problems, and provides a compound having a weight average molecular weight of 1000 to 13000 and represented by the following chemical formula 1:
chemical formula 1:
Figure BDA0001413439660000021
in the above chemical formula 1, R1Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, and B is
Figure BDA0001413439660000022
Figure BDA0001413439660000023
A1、A2And A3Each independently is a hydrogen atom,
Figure BDA0001413439660000024
Figure BDA0001413439660000031
A above1、A2And A3At least one of which is not a hydrogen atom, n, m and k are each independently a rational number of 0 to 8, l is a rational number of 0.1 to 12, A4Is a hydrogen atom,
Figure BDA0001413439660000032
Figure BDA0001413439660000033
R is as defined above2Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, the R is3Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, i is a rational number of 0-8, j is a rational number of 0.1-8, R is4Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, o is a rational number of 0-8, p is a rational number of 0.1-8, R is5Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, provided that R is7And R8Are each a hydrogen atom or R7And R8One of them is a hydrogen atom and the other is a methyl group.
Further, according to an embodiment of the present invention, R is1、R2、R3、R4And R5Each independently represents an alkyl group having 4 or less carbon atoms or a substituted or unsubstituted aryl group, and the aryl group may be selected from the group consisting of a phenyl group, a biphenyl group, a naphthalene group, an anthracene group, a phenanthrene group, a pyrene group, a perylene group, a substituted or unsubstituted aryl group,
Figure BDA0001413439660000041
(chrysene) group, cresol (cresol) group and fluorene (fluoroene) group.
Further, according to an embodiment of the present invention, R is1、R2、R3、R4And R5Each independently may be unsubstituted phenyl, naphthyl or biphenyl.
Also provided is a curing agent for epoxy resins, which contains a copolymer having a weight average molecular weight (Mw (molecular weight)) of 1000 to 13000, as a copolymer obtained by copolymerizing monomers represented by the following chemical formula 2, chemical formula 3 and chemical formula 4.
Chemical formula 2:
Figure BDA0001413439660000042
in the chemical formula 2, a is a rational number of 0 to 8, and if R is7And R8Are each a hydrogen atom or R7And R8One of them is a hydrogen atom and the other is a methyl group.
Chemical formula 3:
Figure BDA0001413439660000043
in the above chemical formula 3, B is
Figure BDA0001413439660000044
X1Is a halogen atom.
Chemical formula 4:
Figure BDA0001413439660000045
in the above chemical formula 4, X2Is a halogen atom, R6Is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms.
Further, according to an embodiment of the present invention, the X is1And X2Each independently represents one of fluorine atom, chlorine atom, bromine atom and iodine atom6The aryl group may include one or more groups selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, perylene, and the like,
Figure BDA0001413439660000046
A mesityl group and a fluorenyl group.
Further, according to an embodiment of the present invention, R is6May be one selected from the group consisting of unsubstituted phenyl, naphthyl and biphenyl (biphenyl).
Further, according to an embodiment of the present invention, the ratio of 1: 0.1-1.5: 0.1 to 3 molar ratio of the monomer represented by the chemical formula 2, the chemical formula 3 and the chemical formula 4.
The present invention also provides a method for preparing a curing agent for epoxy resin, the method comprising: step 1, with 1: 0.1-1.5: introducing monomers represented by the following chemical formula 2, chemical formula 3 and chemical formula 4 into a reaction tank at a molar ratio of 0.1 to 3; and a step 2 of preparing a copolymer represented by the following chemical formula 1 by reacting the monomer introduced in the step 1.
Chemical formula 2:
Figure BDA0001413439660000051
in the chemical formula 2, a is a rational number of 0 to 8, and if R is7And R8Are each a hydrogen atom or R7And R8One of them is a hydrogen atom and the other is a methyl group.
Chemical formula 3:
Figure BDA0001413439660000052
in the above chemical formula 3, B is
Figure BDA0001413439660000053
X1Is a halogen atom.
Chemical formula 4:
Figure BDA0001413439660000054
in the above chemical formula 4, X2Is a halogen atom, R6Is substituted orAn unsubstituted aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms.
Chemical formula 1:
Figure BDA0001413439660000055
in the above chemical formula 1, R1Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, and B is
Figure BDA0001413439660000056
Figure BDA0001413439660000057
A1、A2And A3Each independently is a hydrogen atom,
Figure BDA0001413439660000058
Figure BDA0001413439660000061
A above1、A2And A3At least one of n, m and k is not a hydrogen atom, n, m and k are each independently a rational number of 0 to 8, l is a rational number of 0.1 to 12, A is4Is a hydrogen atom,
Figure BDA0001413439660000062
Figure BDA0001413439660000063
R is as defined above2Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, the R is3Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, i is a rational number of 0-8, j is a rational number of 0.1-8, R is4Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, o is a rational number of 0-8, p is a rational number of 0.1-8, R is5Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, provided that R is7And R8Are each a hydrogen atom or R7And R8One of them is a hydrogen atom and the other isA methyl group.
Furthermore, according to an embodiment of the present invention, the method may further include: after the reaction of the monomers, water is introduced into the reaction tank to remove salts generated as a reaction by-product, and then the process of separating the prepared curing agent for epoxy resin is performed at least once.
Furthermore, according to an embodiment of the present invention, in the step 2, one or more catalysts selected from the group consisting of triethylamine (triethylamine), trimethylamine (trimethylamine), tripropylamine (tripropylamine), pyridine (pyridine) and N-methylpiperidine (N-methylpiperidine) may be used.
The present invention also provides an electrical/electronic sealing material comprising the above-mentioned curing agent for epoxy resin and epoxy resin.
The present invention also provides a substrate laminate for electric and electronic devices, which comprises the curing agent for epoxy resin and epoxy resin.
The present invention also provides an epoxy resin composition comprising the above-mentioned curing agent for epoxy resin and an epoxy resin.
The cured product of the curing agent for epoxy resin of the present invention has a high glass transition temperature to exhibit excellent thermal stability, and has low moisture absorption to minimize moisture absorption in a semiconductor or the like, thereby preventing internal peeling of the semiconductor, cracks, or the like in a soldering process. Further, the excellent adhesive force and high peel strength significantly increase the durability of the cured product and have a low thermal expansion coefficient, thereby preventing the package from being bent. Further, by significantly improving the dielectric constant, dielectric loss, and the like, high-density integration of semiconductors based on significant improvement in electrical insulation properties can be realized, and thus the semiconductor can be widely used as a sealing material for electric and electronic devices, a laminate material, and the like.
Drawings
FIG. 1 shows an Infrared (IR) spectrum according to an embodiment of the present invention.
FIG. 2 is a Gel Permeation Chromatography (GPC) graph of one embodiment of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains can easily carry out the embodiments. The invention can be implemented in many different ways and is not limited to the embodiments described herein. In the drawings, portions that are not related to the description are omitted for the sake of clarity, and the same reference numerals are given to the same or similar components throughout the specification.
As described above, as a conventional curing agent for epoxy resin, a curing agent having active hydrogen such as amine (amine) compound, phenol (phenol) compound, etc. is often used, but when curing epoxy (epoxy) resin, a polar high hydroxyl group is generated by the reaction of an epoxy group and active hydrogen, which causes a problem that the moisture absorption of the final cured product is increased and electrical characteristics such as dielectric constant and dielectric loss are lowered.
In contrast, in the present invention, the above problems are solved by providing a curing agent for epoxy resins comprising a compound represented by the following chemical formula 1 having a weight average molecular weight (molecular weight) of 1000 to 13000.
Chemical formula 1:
Figure BDA0001413439660000081
in the above chemical formula 1, R1Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, and B is
Figure BDA0001413439660000082
Figure BDA0001413439660000083
A1、A2And A3Each independently is a hydrogen atom,
Figure BDA0001413439660000084
Figure BDA0001413439660000085
A above1、A2And A3At least one of which is not a hydrogen atom, n, m and k are each independently a rational number of 0 to 8, l is a rational number of 0.1 to 12, A4Is a hydrogen atom,
Figure BDA0001413439660000086
Figure BDA0001413439660000087
R is as defined above2Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, the R is3Is aryl group having 6 to 24 carbon atoms or alkyl group having 4 or less carbon atoms, i is a rational number of 0 to 8, j is a rational number of 0.1 to 8, and R is4Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, o is a rational number of 0-8, p is a rational number of 0.1-8, R is5Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, provided that R is7And R8Are each a hydrogen atom or R7And R8One of them is a hydrogen atom and the other is a methyl group.
As described above, the curing agent of the present invention has a high glass transition temperature, is excellent in heat resistance, improves reliability of a cured product due to low moisture absorption, has excellent mechanical properties due to excellent adhesive force and high peel strength, reduces defects in the cured product due to a low thermal expansion coefficient, and realizes an integrated circuit based on improvement in electrical properties such as dielectric constant and dielectric loss.
First, the compound represented by chemical formula 1 will be described.
The curing agent for epoxy resin of the present invention comprises a compound represented by the following chemical formula 1 having a weight average molecular weight (molecular weight) of 1000 to 13000.
Chemical formula 1:
Figure BDA0001413439660000091
in the above chemical formula 1, R1Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, and B is
Figure BDA0001413439660000092
Figure BDA0001413439660000093
A1、A2And A3Each independently is a hydrogen atom,
Figure BDA0001413439660000094
Figure BDA0001413439660000095
(hereinafter, referred to as chemical formula X.)
At this time, not only the above-mentioned A1、A2And A3Are each independently selected from A1、A2And A3One or more of the group of compositions is also independent. For example, in the above chemical formula 1, when n is 4, m is 3, and k is 2, A is contained1Is 4, A2Is 3, A3Is 2, at this time, in each A1Are independent of each other and are also at each A2Are independent of each other and are also at each A3Are independent of each other.
And, in the above A1、A2And A3At least one of which is not hydrogen. If A is above1、A2And A3When a curing agent containing both hydrogen and an epoxy (epoxy) resin are cured, polar high hydroxyl groups are generated by the reaction between an epoxy group and active hydrogen, and therefore, there is a problem that the moisture absorption of the final cured product increases and electrical characteristics such as dielectric constant (Dk) and dielectric loss (Df) decrease.
Further, n, m and k are each independently a rational number of 0 to 8, and more preferably n, m and k are each independently a rational number of 1.5 to 6 in terms of glass transition temperature, heat resistance and electrical characteristics of the cured product. When at least one selected from the group consisting of n, m and k is more than 8, there is a problem that when curing with epoxy, the surface of the cured product becomes uneven, which may cause a problem in adhesion, and thus it is not suitable for use as a laminate or a sealing material.
And l is a rational number of 0.1 to 12. When l is less than 0.1, there are problems that the heat resistance of the cured product is lowered and the glass transition temperature is lowered, and it is difficult to achieve desired physical properties such as lowering of the dielectric constant and the dielectric dissipation factor when curing with epoxy. When l is more than 12, a gelled product may be formed, and when the cured product is cured together with epoxy, the surface of the cured product becomes uneven, which may cause a problem in adhesion, and thus, the cured product may be unsuitable for use as a laminate or a sealing material.
And, in the above chemical formula X, A4Is a hydrogen atom,
Figure BDA0001413439660000101
Figure BDA0001413439660000102
In this case, o is a rational number of 0 to 8, and p is a rational number of 0.1 to 8. More preferably, o and p are each independently a rational number of 2 to 6 in terms of glass transition temperature, heat resistance and electrical characteristics of the cured product. When o and/or p is larger than 8, there is a problem that when curing is performed with epoxy, the surface of the cured product becomes uneven, and there is a possibility that a problem occurs in adhesion, and therefore, the cured product is not suitable for use as a laminate or a sealing material.
In the curing agent for epoxy resin of the present invention, R is as defined above1、R2、R3、R4And R5As the aryl group which may be independently substituted or unsubstituted, respectively, the above aryl group may comprise one or more groups selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, phenanthryl, pyrenyl, perylene, and the like,
Figure BDA0001413439660000111
A compound selected from the group consisting of mesityl, cresyl and fluorenyl, more preferably, the above-mentioned R1、R2、R3、R4And R5Can be respectively and independently arrangedIs 1 selected from the group consisting of unsubstituted phenyl, naphthyl and biphenyl. In the above-mentioned R1、R2、R3、R4And R5Respectively independently selected from the group consisting of unsubstituted phenyl, naphthyl and biphenyl in the chemical formula 1, and the copolymer containing R6Is anthryl, phenanthryl, pyrenyl, perylene group,
Figure BDA0001413439660000112
A cured product obtained by curing a copolymer of a monomer having a fluorene group and a monomer having a fluorene group has a significantly lower dielectric constant, dielectric loss, and the like, and can realize high-density integration of semiconductors with significantly improved electrical insulation properties, and thus can be widely used as a sealing material for electric and electronic devices, a laminate material, and the like.
On the other hand, the weight average molecular weight (molecular weight) of the compound represented by the above chemical formula 1 can be only 1000 to 13000 because the compound represented by the chemical formula 1 of the present invention can have a wide range of molecular weight. Thus, the effect intended by the present invention can be expressed without referring to the compound represented by chemical formula 1.
The reason why the compound represented by chemical formula 1 of the present invention can have a wide range of molecular weight distribution is specifically observed because the polymer (A represented by chemical formula X) that can be randomly determined in molecular weight is contained in the copolymer1、A2And A3) Repeating units of grafting. I.e. in A1In the case of the above chemical formula X, the polymer represented by the chemical formula X further contains a monomer selected from the group consisting of A and A, which may be represented by the chemical formula X1、A2And A3One or more of the group consisting of. This is because, in the copolymerization of the monomer represented by chemical formula 3 and the monomer represented by chemical formula 2, which will be described below, the molecular weight of the polymer represented by chemical formula 2 may be very random depending on the polymerization degree of the polymer, and in addition, the reaction sites that can react with the monomer represented by chemical formula 3, that is, the hydroxyl groups contained in the polymer represented by chemical formula 2 increase as the polymerization degree of the polymer represented by chemical formula 2 increases, so that the polymerization degree of the polymer represented by chemical formula 2 increasesPolymerization can be achieved by reacting each hydroxyl group again randomly with the monomer of chemical formula 3, and thus the molecular weight is very random while having a very wide molecular weight distribution.
In order to do so, the compound represented by chemical formula 1 of the present invention may include a having a molecular weight determined very randomly1(A1a、A1b、A1c… …) and/or A2(A2a、A2b、A2c… …) and/or A3(A3a、A3b、A3c… …), as also described above at A)1a(and/or A)1b、A1c… …) and/or A2a(and/or, A)2b、A2c… …) and/or A3a(and/or A)3b、A3c. … …) may contain A whose molecular weight is determined very randomly in a layer-by-layer graft1a(A1a、 A1b、A1c、……)、A2a(A2a、A2b、A2c… …) and A3a(A3a、A3b、A3c… …) the compound of formula 1 can have a wide range of molecular weight distribution. However, even the compound simply represented by the above chemical formula 1 does not express the physical properties aimed at by the present invention, and the compound having the structural formula of the above chemical formula 1 and satisfying a specific molecular weight is required to express the aimed physical properties.
Accordingly, the weight average molecular weight of the compound represented by the above chemical formula 1 of the present invention satisfies 1000 to 13000, and thus a cured product cured by including the curing agent for epoxy resin of the present invention can simultaneously have excellent heat resistance, high mechanical strength, excellent internal moisture absorption, and significantly improved electrical characteristics. When the weight average molecular weight (molecular weight) of the compound represented by chemical formula 1 is less than 1000, there are problems that the heat resistance of the cured product is lowered and the glass transition temperature is lowered when curing with epoxy, and that the electrical characteristics of the dielectric constant and the dielectric dissipation factor are also lowered, and when the weight average molecular weight is more than 13000, there is a possibility that a gelled product is formed, and when curing with epoxy, the peel strength is lowered, and the surface of the cured product is not uniform, causing a problem in adhesion, and thus there is a problem that it is not suitable for use as a laminate material and a sealing material. According to a preferred embodiment of the present invention, in order to achieve further improved physical properties, the weight average molecular weight of the compound represented by chemical formula 1 may be 5000 to 9000.
Also provided is a curing agent for epoxy resins, which contains a copolymer having a weight average molecular weight (molecular weight) of 1000 to 13000, as a copolymer obtained by copolymerizing monomers represented by the following chemical formula 2, chemical formula 3 and chemical formula 4.
Chemical formula 2:
Figure BDA0001413439660000121
in the chemical formula 2, a is a rational number of 0 to 8, and if R is7And R8Are each a hydrogen atom or R7And R8One of them is a hydrogen atom and the other is a methyl group.
Chemical formula 3:
Figure BDA0001413439660000122
in the above chemical formula 3, B is
Figure BDA0001413439660000123
Chemical formula 4:
Figure BDA0001413439660000124
in the above chemical formula 4, X2Is a halogen atom, R6Is an aryl group having 5 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms.
First, the chemical formula 2 will be described. The monomer represented by the above chemical formula 2 and the monomer represented by the above chemical formula 3 are copolymerized, a is a rational number of 0 to 8, and considering the heat resistance and glass transition temperature of the cured product, it is preferable that the average value is not 0. When the average value of a is more than 8, there is a problem that the surface of the cured product becomes uneven when cured with epoxy, and the adhesion is problematic, and thus the cured product is not suitable for use as a laminate or a sealing material.
According to the present invention, the monomers represented by the above chemical formulas 2 and 3 may be represented by 1: 0.1 to 1.5, preferably 1: 0.5 to 1.2. The cured product using the curing agent of the present invention satisfies the above range, and has advantages of improved heat resistance due to a high glass transition temperature, excellent electrical properties such as dielectric constant and dielectric dissipation factor, and high peel strength, and improved mechanical properties.
In the case where the monomers represented by the above chemical formulas 2 and 3 are represented by a molecular weight of less than 1: when the copolymerization is carried out at a molar ratio of 0.1, there is a possibility that a gelled product is formed, and when the cured product is cured together with epoxy, the peel strength is lowered, and the surface of the cured product is not uniform, which causes a problem in adhesion, and therefore, there is a problem that the cured product is not suitable for use as a laminate or a sealing material. .
Next, the chemical formula 3 will be described. In the monomer represented by the above chemical formula 3, X1The halogen atom may contain one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably, may be a chlorine atom.
The monomer represented by chemical formula 3 is a monomer that is copolymerized with the monomers represented by chemical formulas 2 and 4, and more preferably, the monomer represented by chemical formula 3 may be a monomer represented by chemical formula 3-1 below.
Chemical formula 3-1:
Figure BDA0001413439660000131
x in the above chemical formula 3-11Is a halogen atom.
In the above chemical formula 3-1, two functional groups (-COX1) bonded to a benzene ring have meta (meta) alignment, so that both improved heat resistance and excellent electrical characteristics can be achieved, and internal moisture absorption and a low coefficient of thermal expansion value can be achieved, as compared to the case where two of the above functional groups are ortho (ortho) or para (para) alignment. Specifically, it was confirmed that the glass transition temperature was high and the values of the dielectric constant, the dielectric dissipation factor moisture absorption rate, the Coefficient of Thermal Expansion (CTE) (a1, ppm), and the coefficient of thermal expansion (a2, ppm) were reduced in the case of the cured products obtained in the following examples.
Also, it is preferable that only the monomer represented by chemical formula 3-1 is contained in the monomer represented by chemical formula 3, a part of the monomer represented by chemical formula 3-1 is contained, and the monomer in the case of being aligned in the ortho-position or the para-position is contained as a remaining copolymer, there is a problem that the glass transition temperature is low, and the dielectric constant and the dielectric loss are high.
And, in the case of the above chemical formula 3-1, X is contained as a halogen atom1. In the above-mentioned X1In the case of halogen atoms, the halogen atoms are easily removed by HX gas at low temperature (for example, 60 ℃ or lower) using a catalyst, and the reaction time can be remarkably reduced, so that the reaction can be easily performed in a short time under low temperature conditions, the risk of process progress is reduced, and the productivity can be improved.
Next, the chemical formula 4 will be described. The monomer represented by chemical formula 4 is a monomer included as a terminal chelating agent in the copolymerization reaction of the monomers represented by chemical formulas 2 and 3.
X according to the monomer represented by the above chemical formula 42And R6The type (D) of (D) may be varied depending on the physical properties of a cured product obtained by curing a copolymer obtained by copolymerization of the (D).
According to the invention, X is2Comprising one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, wherein R is6As substituted or unsubstituted aryl or substituted or unsubstituted C1～C4The above aryl group may comprise one or more groups selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, perylene, and the like,
Figure BDA0001413439660000141
A mesityl group and a fluorenyl group. More preferably, R is as defined above6Can be thatUnsubstituted phenyl, biphenyl or naphthyl.
In the above-mentioned R6When it is an unsubstituted phenyl, biphenyl or naphthyl group, the group represented by the above chemical formula 1 is bonded to R6The intermediate contains a compound selected from the group consisting of anthryl, phenanthryl, pyrenyl, perylenyl,
Figure BDA0001413439660000142
A cured product obtained by curing a copolymer of one monomer selected from the group consisting of mesityl, cresyl and fluorenyl groups has a lower dielectric constant and a lower dielectric loss value than those of a cured product obtained by curing a copolymer of one monomer selected from the group consisting of mesityl, cresyl and fluorenyl groups, and thus a cured product having significantly improved electrical characteristics can be obtained.
According to a preferred embodiment of the present invention, the ratio of 1: 0.1-1.5: 0.1 to 3, preferably 1: 0.5-1.2: 1.6 to 2.8.
Can be respectively measured by the following steps of 1: 0.1-1.5: when the monomers represented by the chemical formula 2, the chemical formula 3, and the chemical formula 4 are copolymerized in a molar ratio of 0.1 to 3, the heat resistance is improved by satisfying the above range, and the composition has excellent electrical characteristics such as a dielectric constant and a dielectric dissipation factor, and has an advantage of improving mechanical properties by increasing peel strength.
In the case of the monomers represented by chemical formulas 2 and 3 with a molar ratio of less than 1: when copolymerization is carried out at a molar ratio of 0.1, there may be a problem that the glass transition temperature of the cured product is low and electrical characteristics such as dielectric constant and dielectric dissipation factor are lowered, and when copolymerization is carried out at a molar ratio of more than 1:1.5, there is a possibility that a gelled product is formed, and when curing is carried out with epoxy, peeling strength is lowered and the surface of the cured product is not uniform, causing a problem in adhesion, and therefore, there may be a problem that it is not suitable for use as a laminate or a sealing material.
Next, the present invention provides a method for preparing a curing agent for epoxy resin, the method comprising: step 1, with 1: 0.1-1.5: introducing monomers represented by the following chemical formula 2, chemical formula 3 and chemical formula 4 into a reaction tank at a molar ratio of 0.1 to 3; and a step 2 of preparing a copolymer represented by the following chemical formula 1 by reacting the monomer introduced in the step 1.
Chemical formula 2:
Figure BDA0001413439660000151
in the chemical formula 2, a is a rational number of 0 to 8, and if R is7And R8Are each a hydrogen atom or R7And R8One of them is a hydrogen atom and the other is a methyl group.
Chemical formula 3:
Figure BDA0001413439660000152
in the above chemical formula 3, B is
Figure BDA0001413439660000153
X1Is a halogen atom.
Chemical formula 4:
Figure BDA0001413439660000154
in the above chemical formula 4, X2Is a halogen atom, R6Is a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms.
Chemical formula 1:
Figure BDA0001413439660000155
in the above chemical formula 1, R1Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, and B is
Figure BDA0001413439660000156
Figure BDA0001413439660000157
A1、A2And A3Each independently is a hydrogen atom,
Figure BDA0001413439660000158
Figure BDA0001413439660000159
A above1、A2And A3At least one of n, m and k is not a hydrogen atom, n, m and k are each independently a rational number of 0 to 8, l is a rational number of 0.1 to 12, A is4Is a hydrogen atom,
Figure BDA00014134396600001510
Figure BDA0001413439660000161
R is as defined above2Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, the R is3Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, i is a rational number of 0-8, j is a rational number of 0.1-8, R is4Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, o is a rational number of 0-8, p is a rational number of 0.1-8, R is5Is aryl with 6-24 carbon atoms or alkyl with 4 or less carbon atoms, provided that R is7And R8Are each a hydrogen atom or R7And R8One of them is a hydrogen atom and the other is a methyl group.
The production method of the present invention will be described in detail below by steps.
In the method for producing a curing agent for epoxy resins of the present invention, in step 1, after an organic solvent is charged into a reaction tank to which a nitrogen charging pipe, a thermometer, and a circulation cooler are attached, the reaction tank is heated to a temperature of 1: 0.1-1.5: the monomers represented by the above chemical formula 2, chemical formula 3 and chemical formula 4 are introduced in a molar ratio of 0.1 to 3, more preferably in a ratio of 1: 0.5-1.2: 1.6 to 2.8, and then the monomer represented by the above chemical formula 2, chemical formula 3, and chemical formula 4 is repeatedly copolymerized to prepare chemical formula 1 in the following step.
In the case of the monomers represented by chemical formulas 2 and 3 with a molar ratio of less than 1: when copolymerization is carried out at a molar ratio of 0.1, there may be a problem that the glass transition temperature of the cured product is low and electrical characteristics such as dielectric constant and dielectric dissipation factor are lowered, and when copolymerization is carried out at a molar ratio of more than 1:1.5, there is a possibility that a gelled product is formed, and when curing is carried out with epoxy, the peel strength of the cured product is lowered, the surface of the cured product is not uniform, and a problem occurs in adhesion, and there may be a problem that it is not suitable for use as a laminate or a sealing material.
In this case, when the organic solvent is an organic solvent included in the preparation of the curing agent for epoxy resin, it can be used without limitation, and as a non-limiting example thereof, one or more organic solvents selected from the group consisting of toluene, methyl ethyl ketone, and methyl isobutyl ketone may be used independently or in combination.
In the method for preparing the curing agent for epoxy resin of the present invention, the monomer introduced in the step 1 is completely dissolved at 20 to 40 ℃ under a nitrogen atmosphere in the step 2, and after dropping the catalyst uniformly for 1 to 3 hours, the curing step is performed for 1 to 3 hours, thereby preparing the copolymer represented by the chemical formula 1. In this case, heat generation occurs in the dropping and curing steps, and therefore, it is necessary to perform the reaction at a reaction temperature of 50 ℃ or lower.
The catalyst functions as a catalyst for the reaction and HCl gas generated in the ester process, and a catalyst and an acid trapping agent that can be used in a copolymerization step of a general curing agent may be used, and preferably, one or more selected from the group consisting of triethylamine (triethylamine), trimethylamine (trimethylamine), tripropylamine (tripropylamine), pyridine (pyridine), and N-methylpiperidine (N-methylpiperidine), and more preferably, triethylamine is used. The catalyst may be used independently or in combination with one or more kinds of catalysts.
The preparation method of the curing agent for epoxy resin of the invention also comprises the following steps: after the reaction of the monomers, the step of introducing water into the reaction tank to remove salts formed as reaction by-products and then separating the prepared curing agent for epoxy resin is preferably performed once or more.
The copolymer and the salt formed as the additional product are precipitated by the reaction in the above step 2, and the desalting step can be carried out by adding a solvent such as water to remove the salt formed as the additional product. In the desalting step, specifically, after the salt produced as an additional reaction is dissolved, a liquid separation step may be performed to separate the copolymerized compound, and then the separated copolymerized compound may be vacuum degassed at a temperature of 150 to 200 ℃.
Further, the present invention provides an encapsulating material (encapsulating) for electrical and electronic devices, which is characterized by comprising the curing agent for epoxy resin of the present invention and an epoxy resin.
The present invention also provides a laminate for an electric/electronic substrate, which is characterized by containing the curing agent for an epoxy resin of the present invention and an epoxy resin.
The present invention also provides an epoxy resin composition comprising the curing agent for epoxy resin of the present invention and an epoxy resin.
As the above epoxy resin, a known epoxy resin can be used within a range not impairing the effects of the present invention, and as non-limiting examples thereof, epoxides of 2-valent phenols such as bisphenol a, bisphenol F, bisphenol S, bisphenol fluorene, 2 '-biphenol, 3', 5 '-tetramethyl-4, 4' -dihydroxybiphenol, resorcinol, naphthalene diol and the like can be used independently or in combination with two or more kinds; epoxides of phenols having a valence of 3 or more, such as tris- (4-hydroxyphenyl) methane, 1, 2-tetrakis (4-hydroxyphenyl) ethane, phenol aldehyde, o-cresol aldehyde, and the like; epoxy compounds of copolymerized resins of dicyclopentadiene and phenols, epoxy compounds of biphenyl aralkyl type phenol resins synthesized from phenols, dichloromethyl biphenyl, and the like, epoxy compounds derived from naphthol aralkyl resins synthesized from naphthols, p-xylene dichloride, and the like.
However, according to a preferred embodiment of the present invention, in order to express excellent electrical characteristics, internal moisture absorption, improved peel strength, and heat resistance, the Epoxy resin may include one or more selected from the group consisting of o-phenylphenol Novolac Epoxy (ortho-phenylphenol Novolac Epoxy), an Epoxy type of a copolymerized resin of dicyclopentadiene and phenol, and an oxide type of a biphenyl aralkyl type phenol resin synthesized from dichloromethyl biphenyl, and the like, and the cured sealing material or laminate may have a dielectric constant (Dk) of 3.0 or less and a dielectric loss of 0.01 or less at a frequency of 1GHz, and this improved electrical insulation characteristic has an advantage of achieving high speed of devices by high integration of semiconductors in integrated circuit substrates, printed circuit boards, and the like.
In addition, in order to improve the physical properties of the cured product, an inorganic filler may be added in addition to the epoxy resin and the curing agent of the present invention. When an inorganic filler is blended, physical properties such as internal moisture absorption can be improved, and when an inorganic filler is included, the composition is suitable for sealing. As the inorganic filler, a general electric and electronic sealing material or an inorganic charging material used for a laminate material for an electric and electronic substrate can be used without limitation, and as non-limiting examples thereof, silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, stearate, spinel, mullite, titania, or the like can be used, and two or more kinds thereof can be used independently or in combination, and preferably, fused silica is used as a main component, and the form thereof can be a crushed form or a spherical form. Generally, as the silica, silica having several particle diameter distributions is used in combination. Preferably, the silica which can be combined has an average particle diameter in the range of 0.5 to 100. mu.mm. When the inorganic filler is blended, the content is preferably 83 weight% or more, and more preferably 83 to 90 weight%. If the content is less than 83% by weight, the content of the organic component may be high, and the moisture resistance and the low linear expansibility may not be sufficiently exhibited.
Further, an oligomer or polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, phenoxy resin, or the like may be appropriately blended as necessary, and an additive such as a pigment, a flame retardant, a thixotropy imparting agent, a coupling agent, or a fluidity improving agent may be blended.
Examples of the pigment include organic or inorganic extender pigments and flake pigments. Examples of the thixotropy imparting agent include silicones, castor oils, fatty amide waxes, oxidized polyethylene waxes, and organic bentones. And may be compounded with a curing accelerator such as amines, imidazoles, organophosphines, Lewis acids, etc., as required. The amount of the curing accelerator is preferably 0.2 to 5 parts by weight per 100 parts by weight of the epoxy resin.
Further, a release agent such as carnauba wax, OP wax, etc. may be blended as necessary; coupling agents such as gamma-glycidoxypropyltrimethoxysilane and the like; colorants such as carbon black and the like; flame retardants such as antimony trioxide and the like; low stress agents, such as petroleum, and the like, lubricants, such as calcium stearate, and the like.
The sealant composition of the curing agent for epoxy resin of the present invention can be cured by a molding method such as injection molding, compression molding, or transfer molding, to obtain a sealant according to a preferred embodiment of the present invention. Preferably, the resin can be obtained by transfer molding, and the temperature at which a cured product is formed may be 120 to 220 ℃.
Hereinafter, the present invention will be described more specifically by the following examples. At this time, the following examples are presented only for the convenience of understanding, and do not limit the scope of the present invention.
Examples
EXAMPLE 1 preparation of curing agent for epoxy resin
Step 1: 1450g of toluene, 306g of a monomer represented by the following chemical formula 2-1 (0.45 mol), 81.2g of a monomer represented by the following chemical formula 3-2 (0.4 mol) and 168.68g of a monomer represented by the following chemical formula 4-1 (1.2 mol) were introduced into a reaction vessel to which a nitrogen inlet tube, a thermometer and a loop cooler were attached as organic solvents.
Step 2: the monomers represented by the following chemical formulae 2-1, 3-2 and 4-1 introduced in the above step 1 were completely dissolved under the condition of nitrogen gas introduction and a temperature of 30 ℃, and 202.38g of triethylamine (2 moles) was uniformly dropped for 2 hours, and then a ripening step was performed for 2 hours, and when the dropping and ripening step was performed, the reaction temperature did not exceed 50 ℃.
In this case, after a desalting step was performed by adding 350g of water to remove the salt formed as an additive, the desalting step was performed again in the same manner as described above to remove the salt which may remain after the separation of the curing agent compound, and then a liquid separation step was performed. Then, the separated curing agent compound was vacuum-degassed at a temperature of 180 ℃ to obtain 435g of a brown solid curing agent for epoxy resin shown in the following table 1 having a weight average molecular weight (molecular weight) of 5450.
Chemical formula 2-1:
Figure BDA0001413439660000191
and b is 2.
Chemical formula 3-2:
Figure BDA0001413439660000201
chemical formula 4-1:
Figure BDA0001413439660000202
EXAMPLE 2 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, and 306g (0.45 mol), 97.45g (0.48 mol) and 146.19g (1.04 mol) of the monomers represented by the above chemical formula 2-1, chemical formula 3-2 and chemical formula 4-1 were charged to obtain 440g of a curing agent for epoxy resins shown in Table 1 below having a weight average molecular weight (molecular weight) of 7180 as a brown solid.
EXAMPLE 3 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, and 306g (0.45 mol), 107.6g (0.53 mol) and 132.13g (0.94 mol) of the monomers represented by the above chemical formula 2-1, chemical formula 3-2 and chemical formula 4-1 were charged, respectively, to obtain 438g of a brown solid curing agent for epoxy resins shown in Table 1 below having a weight average molecular weight (molecular weight) of 8737.
EXAMPLE 4 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, a monomer represented by the following chemical formula 3-3 was charged instead of the monomer represented by the above chemical formula 3-2 to obtain 428g of a brown solid curing agent for epoxy resin shown in the following table 1 having a weight average molecular weight (molecular weight) of 5670.
Chemical formulas 3 to 3:
Figure BDA0001413439660000203
EXAMPLE 5 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, and instead of the monomer represented by the above chemical formula 3-2, a monomer represented by the following chemical formula 3-4 was charged to obtain 420g of a brown solid curing agent for epoxy resin shown in the following table 1, having a weight average molecular weight (molecular weight) of 5530.
Chemical formulas 3 to 4:
Figure BDA0001413439660000211
EXAMPLE 6 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, and 40.6g (0.2 mol) of the monomer represented by the following chemical formula 3-2 and 40.6g (0.2 mol) of the monomer represented by the following chemical formula 3-4 were charged instead of 81.2g (0.4 mol) of the monomer represented by the above chemical formula 3-2 to obtain 410g of the curing agent for epoxy resins shown in Table 1 below having a weight average molecular weight (molecular weight) of 5510 as a brown solid.
EXAMPLE 7 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, instead of 168.68g (1.2 mol) of the monomer represented by the above chemical formula 4-1, 228.756g (1.2 mol) of the monomer represented by the following chemical formula 6 was charged to obtain 455g of a brown solid curing agent for epoxy resins shown in the following table 1, having a weight average molecular weight (molecular weight) of 7557.
Chemical formula 6:
Figure BDA0001413439660000212
EXAMPLE 8 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, instead of 168.68g (1.2 mol) of the monomer represented by the above chemical formula 4-1, 228.756g (1.2 mol) of the monomer represented by the following chemical formula 6-1 was charged to obtain 467g of a brown solid curing agent for epoxy resins shown in the following Table 1, the weight average molecular weight (molecular weight) of which was 7323.
Chemical formula 6-1:
Figure BDA0001413439660000221
EXAMPLE 9 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, instead of 168.68g (1.2 mol) of the monomer represented by the above chemical formula 4-1, 94.188g (1.2 mol) of the monomer represented by the following chemical formula 8 was charged to obtain 360g of a curing agent for epoxy resins shown in the following table 1, which is a brown solid having a weight average molecular weight (molecular weight) of 4395.
Chemical formula 8:
Figure BDA0001413439660000222
EXAMPLE 10 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, 111.024g (1.2 mol) of a monomer represented by the following chemical formula 8-1 was charged instead of 168.68g (1.2 mol) of the monomer represented by the above chemical formula 4-1 to obtain 378g of a curing agent for epoxy resin of the following table 1 having a brown solid color and a weight average molecular weight (molecular weight) of 4620.
Chemical formula 8-1:
Figure BDA0001413439660000223
EXAMPLE 11 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, 111.648g (0.4 mol) of a monomer represented by the following chemical formula 3-5 was charged instead of the monomer represented by the above chemical formula 3-2 to obtain 451g of a brown solid curing agent for epoxy resins shown in the following Table 1, having a weight average molecular weight (molecular weight) of 7710.
Chemical formulas 3 to 5:
Figure BDA0001413439660000224
comparative example 1 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, 306g (0.45 mol), 4.06g (0.02 mol) and 275.517g (1.96 mol) of the monomers represented by the above chemical formula 2-1, chemical formula 3-2 and chemical formula 4-1 were charged to obtain 467g of the curing agent for epoxy resins shown in Table 1 below as a brown solid having a weight average molecular weight (molecular weight) of 750.
Comparative example 2 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, and 306g (0.45 mol), 182.718g (0.9 mol) and 28.114g (0.2 mol) of the monomers represented by the above chemical formula 2-1, chemical formula 3-2 and chemical formula 4-1 were charged, respectively, to obtain 402g of a brown solid curing agent for epoxy resins shown in Table 1 below having a weight average molecular weight (molecular weight) of 15951.
Comparative example 3 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, 206g (0.677 mol) of a monomer represented by the following chemical formula 9 was charged instead of the monomer represented by the above chemical formula 2-1 to obtain 339g of a brown solid curing agent for epoxy resin shown in the following table 1 having a weight average molecular weight (molecular weight) of 2057.
Chemical formula 9:
Figure BDA0001413439660000231
in this case, n is 1.
Comparative example 4 preparation of curing agent for epoxy resin
Prepared in the same manner as in example 1, 228.29g (1.0 mol) of a monomer represented by the following chemical formula 10 was charged instead of the monomer represented by the above chemical formula 2-1 to obtain 347g of a brown solid curing agent for epoxy resins shown in the following table 1 having a weight average molecular weight (molecular weight) of 1035.
Chemical formula 10:
Figure BDA0001413439660000232
TABLE 1
Figure BDA0001413439660000233
Figure BDA0001413439660000241
Examples of the experiments
Varnishes were prepared by mixing Epoxy resins (Ortho-Phenylphenol Novolac Epoxy Resin (Ortho-Phenylphenol-Novolac Resin), SE-5000, 250g/eq per Epoxy, nova T & C) and the curing agents of examples 1 to 11 and comparative examples 1 to 4 and the curing agent based on the following table 2 in an equivalent ratio, respectively, as shown in the following tables 3 to 5 and C11Z (curing accelerator, 2-undecylimidazole (2-undecylimidizazole)). Thereafter, a press machine (Automatic molding press machine of Simplimet 1000) of "BUEHLER" company was used to mold a formulation, to prepare a cured product, and the following physical properties were measured to show the results in tables 3 to 5.
As the molding operation, curing was performed at 180 ℃ under a pressure of 80bar for 20 minutes, cooling was performed with water for 10 minutes, and then post-curing was performed at 180 ℃ for 2 hours.
TABLE 2
Figure BDA0001413439660000242
Evaluation of physical Properties
1. Dielectric Constant (Dielectric Constant) and Dissipation Factor (Dissipation Factor)
The lower the resin, the more excellent the electrical characteristics of the cured product as measured by JIS-C-6481 using Agilent E4991A radio Impedance/Material Analyzer (Agilent E4991ARF Impedance/Material analyzer).
2. Glass transition Temperature (Tg) and Mass reduction Temperature (5% Weight Loss Temperature, Td)
The glass transition temperature and the 5% mass loss temperature (Td) of the cured product were measured by a Differential Scanning Calorimeter (DSC), and as the 5% mass loss temperature of the cured product, the temperature at which the weight loss of the cured product became 5% was measured by a thermogravimetric analyzer (TGA) at 10 degrees per minute.
3. Moisture Absorption (Water Absorption, weight percent)
As the moisture absorption rate, the cured product was allowed to stand in boiling water at 100 ℃ for 2 hours and then measured as the weight gain (weight percentage). The lower the moisture absorption rate, the more excellent the physical properties of the cured product.
4. Peel Strength (1/2 ounce copper glass Strength (1/2oz copper Peer Strength))
The peel strength was measured by the gIS C-6417 method. The greater the peel strength, the more excellent the mechanical strength.
5. Coefficient of thermal expansion (CTE, ppm/. degree. C.)
As the coefficient of thermal expansion (CTE, ppm/. degree. C.), the coefficients of thermal expansion before and after the glass transition temperature were measured by the method of ASTM E831 using a TMA (Mettler Toedo) apparatus and are shown as a1 and a2, respectively. The smaller the thermal expansion coefficient value, the less the semiconductor package is subjected to a warp phenomenon (warp).
TABLE 3
Figure BDA0001413439660000251
Figure BDA0001413439660000261
TABLE 4
Figure BDA0001413439660000262
TABLE 5
Figure BDA0001413439660000263
Specifically, as can be seen from table 3 above, in the case of the cured products (cured product 1 to cured product 3) obtained in examples 1 to 3, the glass transition temperature was higher and the values of the dielectric constant, dielectric dissipation factor, moisture absorption rate, thermal expansion coefficient (a1, ppm) and thermal expansion coefficient (a2, ppm) were significantly lower than those of the cured products (cured product 4 to cured product 5) obtained in examples 4 to 5.
Further, it was confirmed that the cured products 1 to 3 obtained in examples 1 to 3 had lower dielectric constants and dielectric losses and lower moisture absorption rates, thermal expansion coefficients (a1, ppm) and thermal expansion coefficients (a2, ppm) than the cured product 6 obtained in example 6. Further, it was confirmed that the glass transition temperature was high.
Further, it was confirmed that the dielectric constant and the dielectric loss were lower in the cured products of examples 1 to 3 than in the cured products of examples 7 to 8. On the contrary, the glass transition temperature of the cured products of examples 1 to 3 was low, and the values of the thermal expansion coefficient (a1, ppm) and the thermal expansion coefficient (a2, ppm) were high.
Further, it was confirmed that the dielectric constant and the dielectric loss were equivalent to those of the cured products of examples 9 to 10, but the glass transition temperature was low and the values of the thermal expansion coefficient (a1, ppm) and the thermal expansion coefficient (a2, ppm) were high, as compared with the cured products of examples 1 to 3.
Further, it was confirmed that the cured products of example 11 had a lower dielectric loss but a higher dielectric constant than the cured products of examples 1 to 3.
As can be seen from tables 3 to 5, it was confirmed that by using the curing agents 1 to 7 such as phenol novolac (curing agent 1) and the curing agents of comparative examples 1, 2, 3 and 4, the cured products cured by the curing agents of examples had significantly higher dielectric constant, dielectric loss and moisture absorption rate than the cured products cured by the curing agents of examples, and the glass transition temperature of some of the comparative compounds (comparative cured product 4, comparative cured product 5 and comparative cured product 8) was also significantly lower.
Further, when the cured product 4, the cured product 5, and the cured product 9 were compared, the peel strength was also significantly low, and it was confirmed that the mechanical properties were not good.

Claims (13)

1. A curing agent for epoxy resin, characterized by comprising a compound represented by the following chemical formula 1 having a weight average molecular weight of 1000 to 13000:
chemical formula 1:
Figure FDA0002284222960000011
in the above chemical formula 1, R1An aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms,
b is
Figure FDA0002284222960000012
A1、A2And A3Each independently is a hydrogen atom,
Figure FDA0002284222960000013
Or
Figure FDA0002284222960000014
A above1、A2And A3At least one of which is not a hydrogen atom, n, m and k are each independently a rational number of 0 to 8, l is a rational number of 0.1 to 12,
A4is a hydrogen atom,
Figure FDA0002284222960000015
Figure FDA0002284222960000016
Figure FDA0002284222960000021
R is as defined above2Has 6 to 24 carbon atomsAn aryl group or an alkyl group having 4 or less carbon atoms,
r is as defined above3Is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, i is a rational number of 0 to 8, j is a rational number of 0.1 to 8,
r is as defined above4Is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, o is a rational number of 0 to 8, p is a rational number of 0.1 to 8,
r is as defined above5An aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms,
if the above-mentioned R is7And R8Are each a hydrogen atom or R7And R8One of them is a hydrogen atom and the other is a methyl group.
2. The curing agent for epoxy resin according to claim 1, wherein R is1、R2、R3、R4And R5Each independently is an alkyl group having 4 or less carbon atoms or a substituted or unsubstituted aryl group, and the aryl group includes groups selected from the group consisting of phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, perylene, and the like,
Figure FDA0002284222960000023
A mesityl group and a fluorenyl group.
3. The curing agent for epoxy resin according to claim 2, wherein R is1、R2、R3、R4And R5Each independently unsubstituted phenyl, naphthyl or biphenyl.
4. A curing agent for epoxy resins, which is a copolymer obtained by copolymerizing monomers represented by the following chemical formula 2, chemical formula 3 and chemical formula 4, and is characterized by comprising a copolymer having a weight-average molecular weight of 1000 to 13000:
chemical formula 2:
Figure FDA0002284222960000022
in the chemical formula 2, a is a rational number of 0 to 8, and if R is7And R8Are each a hydrogen atom or R7And R8One of them is a hydrogen atom and the other is a methyl group,
chemical formula 3:
Figure FDA0002284222960000031
in the above chemical formula 3, B is
Figure FDA0002284222960000032
X1Is a halogen atom, and is a halogen atom,
chemical formula 4:
Figure FDA0002284222960000033
in the above chemical formula 4, X2Is a halogen atom, R6Is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms.
5. The curing agent for epoxy resin according to claim 4, wherein X is1And X2Each independently is one of fluorine atom, chlorine atom, bromine atom and iodine atom,
r is as defined above6Is an aromatic group, and the aromatic group,
the aryl group comprises a group selected from phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl,
Figure FDA0002284222960000034
A mesityl group and a fluorenyl group.
6. The curing agent for epoxy resin according to claim 5, wherein R is6Is one of unsubstituted phenyl, naphthyl and biphenyl.
7. The curing agent for epoxy resin according to claim 4, wherein the ratio of 1: 0.1-1.5: and (b) copolymerizing monomers represented by the chemical formula 2, the chemical formula 3, and the chemical formula 4 at a molar ratio of 0.1 to 3.
8. A method for preparing a curing agent for epoxy resin is characterized by comprising the following steps:
step 1, with 1: 0.1-1.5: introducing monomers represented by the following chemical formula 2, chemical formula 3 and chemical formula 4 into a reaction tank at a molar ratio of 0.1 to 3; and
step 2 of preparing a copolymer represented by the following chemical formula 1 by reacting the monomers introduced in the above step 1:
chemical formula 2:
Figure FDA0002284222960000041
in the chemical formula 2, a is a rational number of 0 to 8, and if R is7And R8Are each a hydrogen atom or R7And R8One of them is a hydrogen atom and the other is a methyl group,
chemical formula 3:
Figure FDA0002284222960000042
in the above chemical formula 3, B is
Figure FDA0002284222960000043
X1Is a halogen atom, and is a halogen atom,
chemical formula 4:
Figure FDA0002284222960000044
in the above chemical formula 4, X2Is a halogen atom, R6Is a substituted or unsubstituted aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms,
chemical formula 1:
Figure FDA0002284222960000045
in the above chemical formula 1, R1An aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms,
b is
Figure FDA0002284222960000046
A1、A2And A3Each independently is a hydrogen atom,
Figure FDA0002284222960000047
Figure FDA0002284222960000051
A above1、A2And A3At least one of which is not a hydrogen atom, n, m and k are each independently a rational number of 0 to 8, l is a rational number of 0.1 to 12,
A4is a hydrogen atom,
Figure FDA0002284222960000052
Figure FDA0002284222960000053
R is as defined above2An aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms,
r is as defined above3Is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, i is a rational number of 0 to 8, j is a rational number of 0.1 to 8,
r is as defined above4Is an aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms, o is a rational number of 0 to 8, p is a rational number of 0.1 to 8,
r is as defined above5An aryl group having 6 to 24 carbon atoms or an alkyl group having 4 or less carbon atoms,
if the above-mentioned R is7And R8Are each a hydrogen atom or R7And R8One of them is a hydrogen atom, thenThe other is methyl.
9. The method for preparing a curing agent for epoxy resin according to claim 8, further comprising the steps of: after the reaction of the monomers, water is introduced into the reaction tank to remove salts generated as a reaction by-product, and then the process of separating the prepared curing agent for epoxy resin is performed at least once.
10. The method of claim 8, wherein at least one catalyst selected from the group consisting of triethylamine, trimethylamine, tripropylamine, pyridine and N-methylpiperidine is used in the step 2.
11. An electrical/electronic sealing material, comprising:
the curing agent for epoxy resin according to any one of claims 1 to 7; and
and (3) epoxy resin.
12. A substrate laminate for electric and electronic use, comprising:
the curing agent for epoxy resin according to any one of claims 1 to 7; and
and (3) epoxy resin.
13. An epoxy resin composition, comprising:
the curing agent for epoxy resin according to any one of claims 1 to 7; and
and (3) epoxy resin.
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