JP7417628B2 - Epoxy resin, method for producing the same, and epoxy resin composition containing the same - Google Patents

Description

The present invention ensures excellent heat resistance, high flexibility (low modulus at high temperature), low coefficient of thermal expansion (low CTE), and high refractive index, while improving workability, storage stability, fluidity, and smoothness. The present invention relates to an amorphous fluorene-based epoxy resin with improved properties, a method for producing the same, an epoxy resin composition and a method for producing the same, a laminate and a method for producing the same.

Epoxy resins are used in a variety of fields, including package substrates (IC substrates) on which silicon chips are mounted, EMC sealants, underfills, die bonding materials that bond chips and substrates, solder resists, conductive pastes, and PCBs. It is a core organic material for semiconductor packaging, and is still widely used today due to its excellent heat resistance, insulation properties, chemical resistance, and mechanical properties.

However, in recent years, with the rapid development of semiconductor packaging technology, there has been increasing interest in developing new epoxy materials for next-generation packaging, while recognizing the limitations of existing epoxy materials. Furthermore, as electronic products become smaller, lighter, and more sophisticated, semiconductor chips become thinner, and problems that cannot be solved by conventional epoxy resin compositions arise due to increased integration and surface mounting. In particular, in the case of packaging in which multiple thin chips are stacked to achieve thinness and high functionality, there continues to be a demand for the development of new epoxy materials. For example, as semiconductor packaging technology, which focuses on protection and connection functions for semiconductor integrated circuits (ICs), advances in the direction of system integration, there is a need for the development of materials that can efficiently reduce the stress that is applied to the substrate. Therefore, epoxy material technology with even higher performance in terms of mounting reliability (CTE, warpage, mechanical properties) is required.

Generally, bisphenol A type epoxy resin is widely known as an epoxy resin, and as a solid epoxy resin, one whose molecular weight is increased by subjecting bisphenol A type epoxy resin to a condensation reaction is used. Polymeric epoxy resins may cause blocking. For these reasons, novolak type solid epoxy resins are widely used, but such high molecular weight resins have the disadvantage of high viscosity and poor fluidity and smoothness. In addition, tetramethylbiphenol diglycidyl ether, triglycidyl isocyanurate, and the like have been proposed, but while these all have excellent storage stability, their cured products have a high modulus of elasticity and lack flexibility.

On the other hand, bisphenol fluorene type phenol resins are known to exhibit excellent properties such as heat resistance. Such 9,9-bis(4-hydroxyphenyl)fluorene (9,9-Bis(4-hydroxyphenyl)fluorene), 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (9,9 -Bis[4-(2-hydroxyethoxy)phenyl]fluorene) are also known for use in epoxy resins. Epoxy resins having a fluorene structure can have improved properties such as heat resistance and flexibility compared to conventional bisphenol-type epoxy resins. However, since it has crystallization properties, it has problems such as decreased solubility in solvents and precipitation resulting in decreased storage stability, or decreased workability due to its high melting point. Most crystalline polymer materials have a spherulite structure in which thin layers of lamellar structures are assembled inside, and the fine structure inside the lamella differs depending on the chain structure of each polymer material. In these crystal structures, the molecules have the smallest volume, so they are densely arranged and physically bonded strongly, so from the viewpoint of physical properties, they have high strength, high melting temperature, and are not very soluble in solvents. However, the field of application is very limited, and the workability and storage stability are generally very poor. Further, due to the shrinkage phenomenon associated with the formation process of the crystal structure, warpage may occur when molding a thin product, which needs to be improved.

Further, when the fluorene compound exists simply as a dimer, there is a problem that the viscosity is too high and fluidity and smoothness are reduced. Epoxy compounds have been introduced into the dimer structure of such fluorene-based compounds, but epoxy compounds with such a dimer structure are difficult to mold into resin, are prone to defects, and have limited compatibility and workability. There are disadvantages.

On the other hand, when a fluorene-based epoxy resin composition having a high glass transition temperature is used, there is a problem that the elastic modulus increases greatly, making it vulnerable to external stress due to heat or external impact. Therefore, a non-fluorene-based epoxy compound was mixed and used, but in this case, although the balance of shrinkage rate, elastic modulus, and moldability was improved, the high flexibility, high refraction, and high heat resistance of the fluorene-based epoxy resin There is a problem that the inherent characteristics of

Therefore, in order to ensure the processability and reliability of electronic components during the production of epoxy resins used in polymer materials, the polymer crystallinity should be adjusted to the optimum point to provide excellent thermal stability, high flexibility, and low There is a further need for the development of epoxy resins that have advantages in physical properties such as a coefficient of thermal expansion, as well as good workability, storage stability, and fluidity.

The present invention has a three-dimensional and bulky cardo structure, ensuring excellent heat resistance, low modulus at high temperature, low coefficient of thermal expansion (low CTE), and high refractive index. However, the present invention provides an amorphous fluorene-based epoxy resin with improved workability, storage stability, fluidity, and smoothness, and a method for producing the same.

The present invention also provides an epoxy resin composition containing the amorphous fluorene-based epoxy resin and a method for producing the same.

The present invention also provides a laminate including a resin layer made of the epoxy resin composition, and a method for manufacturing the same.

前記化学式１中、
Ｒ_１およびＲ_２はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基であり、

前記繰り返し単位１中、
ｎは２≦ｎ≦１０の範囲を満たす値であり、
Ｒ_３およびＲ_４はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基である。 According to one embodiment of the present invention, the novolak-type fluorene-based epoxy compound includes a fluorene-based epoxy compound represented by the following chemical formula 1 and a novolak-type fluorene-based epoxy compound containing the following repeating unit 1, and a novolak-type fluorene-based epoxy compound containing the following repeating unit 1. A non-crystalline fluorene-based epoxy resin is provided that contains 3% to 80% of the compound based on the total weight.

In the chemical formula 1,
R ₁ and R ₂ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 10 carbon atoms; 20 cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

In the repeating unit 1,
n is a value satisfying the range of 2≦n≦10,
R ₃ and R ₄ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 10 carbon atoms; 20 cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

Further, the present invention provides a method for producing the above-mentioned amorphous fluorene-based epoxy resin.

The present invention also provides an epoxy resin composition containing the amorphous fluorene-based epoxy resin composition, a curing agent, a curing catalyst, and a solvent.

Further, the present invention provides a laminate including a substrate and a resin layer located on one or both surfaces of the substrate, and the resin layer is made of the epoxy resin composition as described above.

According to the present invention, the amorphous fluorene has improved workability, storage stability, fluidity, and smoothness while ensuring excellent heat resistance, high flexibility, low coefficient of thermal expansion, and high refractive index. epoxy resins are provided.

FIG. 2 is a diagram showing a differential scanning calorimetry (DSC) analysis graph for the fluorene-based biphenol resin of Example 1-1 produced according to an embodiment of the present invention. FIG. 2 is a diagram showing a differential scanning calorimetry (DSC) analysis graph for the conventionally known 4,4'-(9-fluorenylidene) diphenol compound of Comparative Example 1-1. FIG. 2 is a diagram showing a gel permeation chromatography (GPC) analysis graph for the fluorene-based biphenol resin of Example 1-1 produced according to an embodiment of the present invention. FIG. 2 is a diagram showing an analytical graph of gel permeation chromatography (GPC) for the conventionally known 4,4'-(9-fluorenylidene) diphenol compound of Comparative Example 1-1.

In the present invention, terms such as first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another component.

Additionally, the terms used herein are merely used to describe particular embodiments and are not intended to limit the invention. A singular expression includes a plural expression unless the context clearly dictates otherwise. As used herein, terms such as "comprising," "comprising," or "having" are intended to specify the presence of the described feature, number, step, component, or combination thereof. It is to be understood that this does not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

As used herein, the terms "about," "substantially," etc. mean at or near that numerical value, given the manufacturing and material tolerances inherent in the recited meaning. It is used as a meaning and to prevent unconscionable infringers from taking undue advantage of disclosures in which precise or absolute numerical values are referred to to aid in understanding the invention.

Also, the terms "steps for" or "steps for" as used herein do not mean "steps for".

As used herein, the term "a combination of these" included in a Markush-style expression means a mixture or combination of one or more components selected from the group consisting of the components listed in the Markush-style expression. However, it means that it includes one or more selected from the group consisting of the above-mentioned components.

および

は、他の置換基に連結される結合を意味する。 In this specification,

and

means a bond connected to another substituent.

As used herein, "substituted" means, unless otherwise defined, that at least one hydrogen in a compound is an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; Alkynyl group, alkylsilyl group having 1 to 10 carbon atoms; cycloalkyl group having 3 to 30 carbon atoms; aryl group having 6 to 30 carbon atoms; heteroaryl group having 1 to 30 carbon atoms; alkoxy group having 1 to 10 carbon atoms; Silane group; alkylsilane group; alkoxysilane group; amine group; alkylamine group; arylamine group; means substituted with ethyleneoxyl group or halogen group.

As used herein, "hetero" means an atom selected from the group consisting of N, O, S and P, unless otherwise defined.

As used herein, the term "alkyl group" means, unless otherwise defined, a "saturated alkyl group" that does not contain any alkenyl or alkynyl groups; or at least one is meant to include all "unsaturated alkyl groups" containing one alkenyl or alkynyl group. The above "alkenyl group" means a substituent in which at least two carbon atoms form at least one carbon-carbon double bond, and the "alkyne group" means a substituent in which at least two carbon atoms form at least one carbon-carbon double bond. - means a substituent forming a carbon triple bond. The alkyl group may be branched, straight chain or cyclic.

The alkyl group is a linear or branched alkyl group having 1 to 20 carbon atoms, and specifically includes a lower alkyl group having 1 to 6 carbon atoms, a middle alkyl group having 7 to 10 carbon atoms, and a lower alkyl group having 1 to 6 carbon atoms. It can be 11 to 20 higher alkyl groups.

For example, a C1-4 alkyl group means that there are 1 to 4 carbon atoms in the alkyl chain, which may include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, selected from the group consisting of sec-butyl and t-butyl.

Typical alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, and the like.

A "cycloalkyl group" is a cyclic alkyl group, and specifically includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like.

"Alkoxy group" is a functional group in which the above-mentioned alkyl group is bonded to an oxy group, that is, an oxygen atom, and specifically includes methoxy group, ethoxy, isopropoxy, n-butoxy, tert-butoxy, phenyloxy, Examples include cyclohexyloxy group.

"Aromatic group" means a substituent in which all elements of a cyclic substituent have p-orbitals, and these p-orbitals form a conjugation. Specific examples include aryl groups and heteroaryl groups.

An "aryl group" includes single ring or fused ring, ie, multi-ring substituents that share adjacent pairs of carbon atoms.

"Heteroaryl group" means an aryl group in which a heteroatom selected from the group consisting of N, O, S and P is contained within the aryl group. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 of the heteroatoms.

Unless otherwise defined herein, "copolymerization" means block copolymerization, random copolymerization, graft copolymerization, or alternating copolymerization; "copolymer" means block copolymerization, It means a random copolymer, a graft copolymer or an alternating copolymer.

Additionally, when a layer or element is referred to herein as being formed "on" a layer or element, it may mean that the layer or element is formed directly on top of the layer or element; It is meant that other layers or elements can be further formed between each layer, on the object, on the substrate.

Since the present invention is susceptible to various modifications and forms, it will be described in detail below with reference to specific embodiments. However, it is to be understood that this is not intended to limit the invention to the particular disclosed form, but is to include all modifications, equivalents, or alternatives falling within the spirit and technical scope of the invention. It won't happen.

Embodiments of the present invention will be described in detail based on the above definitions. However, this is only presented as an example, and the invention is not limited thereby, but is defined only by the scope of the claims below.

As a result of continuous experiments by the present inventors, in order to reduce the crystal irregularity and crystallinity of the -OH group-substituted fluorene compound, the molecular weight distribution of the polymer was determined by the production method described below. By controlling the physical state with minimal deformation through novolak reaction, it has excellent physical properties such as excellent thermal stability, high flexibility, and low coefficient of thermal expansion, and has excellent workability and storage stability. The present invention was completed by confirming that it was possible to provide an amorphous fluorene-based epoxy resin with good fluidity.

The present invention will be explained in more detail below.

Epoxy resin According to an embodiment of the invention, the epoxy resin has improved workability, storage stability, fluidity and smoothness while ensuring excellent heat resistance, high flexibility, low coefficient of thermal expansion, and high refractive index. A non-crystalline fluorene-based epoxy resin is provided.

Specifically, the heat resistance of the epoxy resin is increased by introducing a fluorene structure into the main chain of the epoxy resin as a cardo-based unit that is rigid and has excellent heat resistance and processability. In addition, at the same time as a cardo unit with an out-of-plane structure is introduced, the crystallinity is reduced by adjusting the molar ratio through a novolac reaction, which improves the processability of the material, such as solubility. improves. Furthermore, by adjusting the crystallinity, it is possible to achieve excellent thermal stability as well as high flexibility and refractive index, making it applicable to a variety of fields such as electronic materials that require high functionality.

In particular, the epoxy resin of the present invention is an amorphous solid comprising a fluorene-based epoxy compound and an optimal range of a dimer or a polymer having more than a dimer, in which part of this compound is produced by a novolak reaction. This is what is shown.

前記化学式１中、
Ｒ_１およびＲ_２はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基であり、

前記繰り返し単位１中、
ｎは２≦ｎ≦１０の範囲を満たす値、つまり、ｎは２以上～１０以下の範囲を満たす値であり、
Ｒ_３およびＲ_４はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基である。
特に、前記繰り返し単位１中、ｎは２以上～１０以下の範囲の値であり、具体的には、ｎは２以上～６以下の範囲を満たす値である。特に、ｎは樹脂の成形の改善および相溶性と作業性を改善する側面から２以上または３以上であり得、熱安定性と共に高い柔軟性と低い熱膨張係数などを確保する側面から１０以下であり得る。 More specifically, the amorphous fluorene-based epoxy resin provided in one embodiment of the present invention is a novolac-type fluorene-based epoxy compound containing a fluorene-based epoxy compound represented by the following chemical formula 1 and the following repeating unit 1. and contains 3% to 80% of a novolak-type fluorene-based epoxy compound containing the following repeating unit 1 based on the total weight.

In the chemical formula 1,
R ₁ and R ₂ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 10 carbon atoms; 20 cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

In the repeating unit 1,
n is a value that satisfies the range of 2≦n≦10, that is, n is a value that satisfies the range of 2 or more and 10 or less,
R ₃ and R ₄ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 10 carbon atoms; 20 cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
In particular, in the repeating unit 1, n is a value in the range of 2 or more and 10 or less, and specifically, n is a value that satisfies the range of 2 or more and 6 or less. In particular, n can be 2 or more or 3 or more to improve resin molding, compatibility, and workability, and 10 or less to ensure thermal stability, high flexibility, and a low coefficient of thermal expansion. could be.

前記化学式１ａ中、Ｒ_１およびＲ_２は前記化学式１で定義した通りである。
前記化学式１中、Ｒ_１およびＲ_２はそれぞれ独立して、水素、炭素数１～４のアルキル基、または炭素数６～１２のアリール基であり、好ましくは、Ｒ_１およびＲ_２は水素であり得る。ただし、これは一例に過ぎず、本発明の一実施形態はこれに限定されない。 Preferably, the fluorene-based epoxy compound represented by the chemical formula 1 includes the following chemical formula 1a.

In the chemical formula 1a, R ₁ and R ₂ are as defined in the chemical formula 1.
In the chemical formula 1, R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and preferably R ₁ and R ₂ are hydrogen. could be. However, this is just an example, and one embodiment of the present invention is not limited thereto.

前記繰り返し単位１ａ中、ｎ、Ｒ_３およびＲ_４は前記繰り返し単位１で定義した通りである。 Preferably, the novolak-type fluorene-based epoxy compound containing the repeating unit 1 contains the following repeating unit 1a.

In the repeating unit 1a, n, R ₃ and R ₄ are as defined in the repeating unit 1.

The novolak-type fluorene-based epoxy compound containing the repeating unit 1 has a three-dimensional and bulky cardo structure, and has excellent heat resistance, high flexibility, a low coefficient of thermal expansion, and a high refractive index. It can also improve workability, storage stability, fluidity and smoothness.

In the amorphous fluorene-based epoxy resin of the present invention, the novolac-type fluorene-based epoxy compound containing the repeating unit 1 is based on the total weight, that is, the fluorene-based epoxy compound represented by the chemical formula 1 and the repeating unit Contains 3% to 80% based on the total weight of the novolak-type fluorene-based epoxy compound containing 1, specifically 10% to 75%, or 10% to 70%, or 10% to 60%, or 10%. % to 30%, or 15% to 30%. The content of the novolak-type fluorene-based epoxy compound containing the repeating unit 1 may be 80% or less in view of application to an epoxy intermediate having a low softening point and melt viscosity and high fluidity and smoothness, and a solvent. From the viewpoint of synthesizing a resin that exists in an amorphous state without problems such as decreased storage stability due to decreased solubility and precipitation, or decreased workability due to high melting point, it is 3% or more. obtain.

As an example, the fluorene-based epoxy compound represented by the chemical formula 1 and the novolac-type fluorene-based epoxy compound containing the repeating unit 1 are contained in a weight ratio of 97:3 to 20:80, specifically 90:10 to 25. :75, or 90:10 to 30:70, or 90:10 to 40:60, or 90:10 to 70:30, or 85:15 to 70:30. The molar ratio of the fluorene-based compound represented by the chemical formula 1 and the novolak-type fluorene-based epoxy compound containing the repeating unit 1 is set so that it can be applied to an epoxy intermediate having a low softening point and melt viscosity and high fluidity and smoothness. The weight ratio may be 20:80 or more, and it is in an amorphous state without problems such as decreased solubility in solvents and precipitation resulting in decreased storage stability, or decreased workability due to high melting point. From the aspect of synthesizing existing resins, the weight ratio may be up to 97:3.

Specifically, in the repeating unit 1, R ₃ and R ₄ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and preferably R ₅ and R ₆ can be hydrogen. However, this is just an example, and one embodiment of the present invention is not limited thereto.

On the other hand, the non-crystalline fluorene-based epoxy resin of the present invention can be produced by reacting a fluorene-based compound and formaldehyde at a specific molar ratio (step 1), and then epoxidizing all the hydroxyl groups of the phenol groups, as described below. (Step 2), it is finally obtained.

前記繰り返し単位Ａ中、
ｌは１≦ｌ≦１０の範囲を満たす値、つまり、ｌは１以上～１０以下の範囲を満たす値であり、
Ｒ’およびＲ’’はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基である。
具体的には、前記繰り返し単位Ａ中、ｌは１≦ｌ≦６の範囲を満たす値、つまり、ｌは１以上～６以下の範囲を満たす値であり得る。
また、Ｒ’およびＲ’’はそれぞれ独立して、水素、炭素数１～４のアルキル基、または炭素数６～１２のアリール基であり、好ましくは、Ｒ’およびＲ’’は水素であり得る。ただし、これは一例に過ぎず、本発明の一実施形態はこれに限定されない。 However, in step 2, not all of the hydroxyl groups of the fluorene-based biphenol resin may be epoxidized. Therefore, the final copolymer may include, but is not limited to, the following repeating units A:

In the repeating unit A,
l is a value that satisfies the range of 1≦l≦10, that is, l is a value that satisfies the range of 1 or more and 10 or less,
R' and R'' are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 3 carbon atoms; ~20 cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
Specifically, in the repeating unit A, l may be a value that satisfies the range of 1≦l≦6, that is, l may be a value that satisfies the range of 1 or more and 6 or less.
Further, R' and R'' are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and preferably R' and R'' are hydrogen. obtain. However, this is just an example, and one embodiment of the present invention is not limited thereto.

Meanwhile, the epoxy equivalent weight (EEW) of the amorphous fluorene-based epoxy resin may be from 200 g/eq to 500 g/eq or from 230 g/eq to 480 g/eq. Here, the epoxy equivalent is a value obtained by dividing the number average molecular weight (g/mol) of the resin by the number of epoxy equivalents (eq/mol). The epoxy group in the copolymer is the site where the hydroxyl of the phenol is epoxidized in step 3, and the fact that its content satisfies the above range provides excellent thermal stability as well as high flexibility and refraction. This means that the rate can be achieved.

The non-crystalline fluorene-based epoxy resin may have a number average molecular weight (Mn) of 200 g/mol to 2000 g/mol, and a weight average molecular weight (Mw) of 300 g/mol to 2000 g/mol. Specifically, the number average molecular weight (Mn) of the amorphous fluorene-based epoxy resin is 250 g/mol to 2000 g/mol, or 300 g/mol to 2000 g/mol, or 325 g/mol to 1500 g/mol, or 350 g/mol. /mol to 1250 g/mol, or 400 g/mol to 1000 g/mol. Furthermore, the weight average molecular weight (Mw) of the amorphous fluorene-based epoxy resin is 300 g/mol to 2000 g/mol, or 350 g/mol to 2000 g/mol, or 350 g/mol to 1500 g/mol, or 360 g/mol to It can be 1250 g/mol, or 420 g/mol to 950 g/mol. Further, the molecular weight distribution (Mw/Mn) determined by the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the fluorene biphenol resin is 0.8 to 4.0, or 0. .9 to 2.0, or 0.95 to 1.8, or 1.03 to 1.4.

As an example, the number average molecular weight and weight average molecular weight of the amorphous fluorene-based epoxy resin are measured using gel permeation chromatography (GPC), and the obtained measured values are converted into polystyrene values. could be. As a specific measuring method, a normal method applicable to fluorene-based epoxy resins can be applied.

The amorphous fluorene-based epoxy resin may be amorphous and have a melting point (Tm) of 30°C to 120°C, or 30°C to 100°C, or 30°C to 80°C, or 60°C to 68°C. . This is due to the process added to reduce crystallization, and the melting point of the amorphous fluorene-based epoxy resin is 140°C to 170°C, which is the melting point (Tm) of existing crystalline fluorene-based epoxy resins. This is considered to be significantly lower than that.

Further, the amorphous fluorene-based epoxy resin is an epoxy resin containing 3% to 97% of a bifunctional or higher-functional novolac polymer based on the total weight, and a phenolic curing agent and a glass transition temperature at the time of curing. (Tg) achieves a high glass transition temperature of 180° C. or higher, 180° C. to 250° C., or 183° C. to 200° C., so it has the characteristic of simultaneously achieving a high glass transition temperature and high flexibility.

As an example, the melting point (Tm) and glass transition temperature (Tg) of the amorphous fluorene-based epoxy resin can be measured using a differential scanning calorimeter (DSC). Specifically, by increasing the temperature of the resin sample from below room temperature at a rate of 10°C/min, a changing portion of Heat Flow appears in which endotherm appears with a constant slope on the DSC (manufactured by Mettler) curve. The glass transition temperature (Tg) is the intermediate value between the temperature at which Heat Flow begins to change and the temperature at which it ends, and the melting point is the temperature corresponding to the top of the endothermic peak that corresponds to the bottom of the DSC curve. (Tm).

Further, the amorphous fluorene-based epoxy resin has a characteristic that it is amorphous and has a softening point even at a low melting temperature. Specifically, the softening point (Ts) of the amorphous fluorene-based epoxy resin may be 70°C to 120°C, 80°C to 110°C, 85°C to 105°C, or 88°C to 98°C. Here, the softening point of the amorphous fluorene-based epoxy resin can be measured according to the ASTM E28 standard using a ring and ball method.

Further, the amorphous fluorene-based epoxy resin may have a melt viscosity of 290 cps to 500 cps, 320 cps to 400 cps, or 350 cps to 397 cps. As an example, the melt viscosity is a value measured at 150° C. using a rotational viscometer manufactured by Brookfield.

In addition, the amorphous fluorene-based epoxy resin was measured for crystallization and precipitation at room temperature (RT, 23°C to 25°C) after dissolving a resin sample in a cyclohexanone solvent at a weight ratio of 1:1. During storage, crystals do not precipitate and it has excellent storage stability.

Further, the amorphous fluorene-based epoxy resin has a refractive index (R.I) of 1.61 to 1.639, 1.62 to 1.629, 1.625 to 1.629, 1.6264 to 1. .6289. As an example, the refractive index (R.I) was measured at a wavelength of 404 nm by joining a prism and changing the incident angle of light.

Method for producing epoxy resin In yet another embodiment of the present invention, a method for producing the above-mentioned amorphous fluorene-based epoxy resin is provided.

In particular, according to the present invention, it has a three-dimensional and bulky cardo structure, and while ensuring excellent heat resistance, high flexibility, low coefficient of thermal expansion, and high refractive index, it has excellent workability and storage stability. Provided is a method for effectively producing an amorphous fluorene-based epoxy resin that has improved properties, fluidity, and smoothness.

Specifically, in the present invention, the molar ratio of reactants is optimized within a predetermined range in the Novolac reaction that polycondenses a fluorene compound and formaldehyde, thereby achieving excellent thermal properties while controlling the crystallinity of the final epoxy resin. It has not only stability but also high flexibility and refractive index, and can exhibit good properties in terms of workability, storage stability, fluidity, and smoothness.

前記化学式２中、
Ｒ_５およびＲ_６はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基であり、

前記繰り返し単位２中、
ｍは２≦ｍ≦１０の範囲を満たす値、つまり、ｍは３以上～１０以下の範囲を満たす値であり、
Ｒ_７およびＲ_８はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基である。
特に、前記繰り返し単位２中、ｍは２以上～１０以下の範囲の値であり、具体的には、ｍは２以上～６以下の範囲を満たす値である。特に、ｍは樹脂の成形改善および相溶性と作業性を改善する側面から２以上または３以上であり得、熱安定性と共に高い柔軟性と低い熱膨張係数などを確保する側面から１０以下であり得る。 More specifically, in the presence of an acid catalyst, a fluorene-based biphenol compound represented by the following chemical formula 2 and formaldehyde are reacted at a molar ratio of 2:1 to 10:1 to produce a novolak type containing the following repeating unit 2. producing a fluorene biphenol resin containing a fluorene biphenol compound (step 1); reacting the fluorene biphenol resin with epihalohydrin in the presence of a hydroxide salt (step 2); Provided is a method for producing the above-mentioned non-crystalline fluorene-based epoxy resin.

In the chemical formula 2,
R ₅ and R ₆ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 10 carbon atoms; 20 cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

In the repeating unit 2,
m is a value that satisfies the range of 2≦m≦10, that is, m is a value that satisfies the range of 3 or more and 10 or less,
R ₇ and R ₈ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 10 carbon atoms; 20 cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
Particularly, in the repeating unit 2, m is a value in the range of 2 or more and 10 or less, and specifically, m is a value that satisfies the range of 2 or more and 6 or less. In particular, m may be 2 or more or 3 or more to improve resin molding, compatibility, and workability, and may be 10 or less to ensure thermal stability, high flexibility, and a low coefficient of thermal expansion. obtain.

前記化学式２ａ中、Ｒ_５およびＲ_６は前記化学式２で定義した通りである。 Preferably, the fluorene compound represented by Chemical Formula 2 includes the following Chemical Formula 2a.

In the chemical formula 2a, R ₅ and R ₆ are as defined in the chemical formula 2.

In the chemical formula 2, R ₅ and R ₆ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and preferably R ₅ and R ₆ are hydrogen. could be. However, this is just an example, and one embodiment of the present invention is not limited thereto.

Particularly, in the method for producing the amorphous fluorene-based epoxy resin, the fluorene-based biphenol compound represented by the chemical formula 2 and formaldehyde are used in a molar ratio of 2:1 to 10:1, specifically 2.5:1. ~10:1, or 3:1 to 10:1, or 4.5:1 to 10:1, or 6:1 to 10:1, or 6:1 to 8:1. Features. The reaction molar ratio of the fluorene-based biphenol compound represented by the chemical formula 2 and formaldehyde is 2:1 from the viewpoint of application to an epoxy intermediate with low softening point and melt viscosity and high fluidity and smoothness. Aspects for synthesizing resins that exist in an amorphous state without problems such as decreased solubility in solvents and precipitation resulting in decreased storage stability, or decreased workability due to high melting point. The molar ratio can be up to 10:1.

In the step 1, the step of reacting the fluorene-based biphenol compound represented by the chemical formula 2 with formaldehyde is a step of reacting the fluorene-based biphenol compound represented by the chemical formula 2 with formaldehyde to form a solid phase non-crystalline resin linked by methylene groups as an addition condensate through a novolak reaction in the presence of an acid catalyst. It is characterized by manufacturing.

Specifically, the step of reacting the fluorene biphenol compound represented by Formula 2 with formaldehyde is performed at 100° C. to 140° C. or 115° C. to 125° C. under conditions of 750 Torr to 770 Torr or 755 Torr to 765 Torr. I can do it. For example, the novolak reaction in Step 1 can be carried out for 1 to 10 hours, or 2 to 6 hours under the conditions described above.

In step 1, the acid catalyst is one or more selected from the group consisting of oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, methylsulfonic acid, and acetic acid, and preferably oxalic acid is used. can do. However, this is just an example, and one embodiment of the present invention is not limited thereto.

The acid catalyst is 0.01 to 10 moles, specifically 0.05 to 8 moles, or 0.1 mole, based on 100 moles of the fluorene biphenol compound represented by the chemical formula 2. It can be used in a content of from molar parts to 5 molar parts, or from 0.5 molar parts to 4 molar parts.

On the other hand, the fluorene-based compound obtained by the novolak reaction is an amorphous fluorene-based biphenol resin (novolak-type phenol resin) containing a novolak-type fluorene-based biphenol compound containing the repeating unit 2.

前記繰り返し単位２ａ中、ｍ、Ｒ_７およびＲ_８は前記繰り返し単位２で定義した通りである。
具体的には、前記繰り返し単位２中、Ｒ_７およびＲ_８はそれぞれ独立して、水素、炭素数１～４のアルキル基、または炭素数６～１２のアリール基であり、好ましくは、Ｒ_７およびＲ_８は水素であり得る。ただし、これは一例に過ぎず、本発明の一実施形態はこれに限定されない。 Preferably, the novolak-type fluorene-based biphenol compound containing repeating unit 2 contains the following repeating unit 2a.

In the repeating unit 2a, m, R ₇ and R ₈ are as defined in the repeating unit 2 above.
Specifically, in the repeating unit 2, R ₇ and R ₈ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and preferably R ₇ and R ₈ can be hydrogen. However, this is just an example, and one embodiment of the present invention is not limited thereto.

Further, the fluorene-based biphenol resin may have a number average molecular weight (Mn) of 200 g/mol to 2000 g/mol, and a weight average molecular weight (Mw) of 200 g/mol to 2000 g/mol. Specifically, the number average molecular weight (Mn) of the fluorene-based biphenol resin is larger than the number average molecular weight of the crystalline monomer represented by the chemical formula 1, more specifically, 300 g/mol to 2000 g/mol, or It can be from 400 g/mol to 2000 g/mol, or from 420 g/mol to 1500 g/mol, or from 425 g/mol to 1250 g/mol, or from 425 g/mol to 800 g/mol. Further, the weight average molecular weight (Mw) of the fluorene biphenol resin is larger than the weight average molecular weight of the crystalline monomer represented by the chemical formula 1, more specifically, 300 g/mol to 2000 g/mol, or 400 g/mol. ˜2000 g/mol, or 420 g/mol to 1500 g/mol, or 425 g/mol to 1250 g/mol, or 450 g/mol to 950 g/mol. Further, the molecular weight distribution (Mw/Mn) determined by the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the fluorene biphenol resin is 0.5 to 4.0, or 0. .8 to 2.0, or 0.9 to 1.5, or 1.05 to 1.2.

As an example, the number average molecular weight (Mn) and weight average molecular weight (Mw) of the fluorene-based biphenol resin are measured using gel permeation chromatography (GPC), and the obtained measured values are converted into polystyrene. It can be the same value. As a specific measuring method, a normal method applicable to fluorene biphenol resin can be applied.

Specifically, the fluorene biphenol resin may have a hydroxyl equivalent of 175 g/eq to 250 g/eq, 180 g/eq to 200 g/eq, or 185 g/eq to 190 g/eq. Here, the hydroxyl equivalent weight (OHEW) is a value obtained by dividing the number average molecular weight (g/mol) of the resin by the number of hydroxyl equivalents (eq/mol). If the hydroxyl equivalent in the resin satisfies the above range, it means that excellent thermal stability, high flexibility and refractive index can be achieved through the subsequent epoxidation step.

Further, the fluorene-based biphenol resin may have no melting point (Tm), or may have a melting point (Tm) of 150°C to 230°C, 160°C to 225°C, or 170°C to 222°C. As an example, the melting point (Tm) of the fluorene-based biphenol resin can be measured using a differential scanning calorimeter (DSC). Specifically, the temperature of the resin sample is increased from below room temperature at a rate of 10°C/min, and the temperature corresponding to the top of the endothermic peak corresponding to the bottom of the DSC (manufactured by Mettler) curve is determined as the melting point. (Tm).

Further, the fluorene-based biphenol resin may have no softening point (Ts), or may have a softening point (Ts) of 110°C to 180°C, 120°C to 165°C, or 125°C to 150°C. Here, the softening point of the fluorene-based biphenol resin can be measured according to the ASTM E28 standard using a ring and ball method.

On the other hand, the amorphous fluorene-based biphenol resin (novolak-type phenol resin) obtained by the novolak reaction is reacted with epihalohydrin in the presence of a hydroxide salt (step 2), and the final substance, the amorphous fluorene-based biphenol resin, is reacted with epihalohydrin in the presence of a hydroxide salt. Manufacture epoxy resin.

Specifically, the step of reacting the fluorene-based biphenol resin with epihalohydrin is carried out at 25° C. to 120° C. or 30° C. under a pressure condition of 100 Torr to 300 Torr, or 120 Torr to 200 Torr, or 140 Torr to 180 Torr, or 30 Torr. It can be carried out at a temperature of 120°C to 120°C, or 30°C to 80°C. For example, the epoxidation reaction in Step 2 may be performed under the conditions described above for 0.5 to 10 hours, or 2 to 6 hours, or 3 to 5 hours.

In step 2, the amount of epihalohydrin used may be 1 to 20 times the hydroxyl group of the fluorene-based biphenol resin, and specifically, 4 to 8 times the amount by mole.

Further, the epihalohydrin may be one or more selected from the group consisting of epifluorohydrin, epichlorohydrin, epibromohydrin, epiiodohydrin, and β-methylepichlorohydrin, and specifically Epichlorohydrin can be used.

In step 2, the amount of the hydroxide salt used may be 0.85 to 1.2 times the mole of the hydroxyl group of the phenol resin.

Further, the hydroxide salt may be an alkali metal or alkaline earth metal hydroxide, for example, selected from the group consisting of NaOH, KOH, CsOH, Ca(OH) ₂ , and Mg(OH) ₂ . It can be one or more types. Specifically, NaOH, KOH, etc. can be used. However, this is just an example, and the embodiment of the present invention is not limited thereto.

The hydroxide salt can be used in a solid state or in an aqueous solution state dissolved in water, and specifically, at a pressure of 100 Torr to 300 Torr or 120 Torr to 200 Torr at 25° C. to 120° C. or 30° C. to 120° C. The reaction may be carried out by adding the mixture in small portions over a period of 0.5 to 6 hours or 2 to 5 hours, or by dropping it in a dropwise manner.

Hereinafter, each step of the method for producing an amorphous fluorene-based epoxy resin as described above will be explained using a specific example.

ここで、ｎ’は０≦ｎ’≦１０の範囲を満たす値、つまり、ｎ’は０以上～１０以下、または０以上～６以下、または０以上～５以下の範囲を満たす値である。 The crystalline compound 4,4'-(9-fluorenylidene) diphenol was treated with formaldehyde and novolac in the presence of oxalic acid. A solid polymer resin represented by the following chemical formula A can be produced by this reaction. At this time, the reactivity of 4,4'-(9-fluorenylidene) diphenol can be adjusted by changing the molar ratio of the novolak reaction, and the molecular weight distribution can be confirmed by gel permeation chromatography (GPC) analysis. Then, the softening point (Ts) of the product was measured by the Ring and Ball method. Therefore, crystallinity/non-crystalline characteristics can be controlled by adjusting the content of n'=0 (monomer) in the following, and as an intermediate resin suitable for the synthesis of epoxy resin, the compound represented by the chemical formula A below can be used. 4,4'-(9-Fluorenylidene) diphenol-novolac resin can be produced. At this time, the preferred molar ratio range and process conditions for the novolac reaction are as described above.

Here, n' is a value that satisfies the range of 0≦n'≦10, that is, n' is a value that satisfies the range of 0 or more and 10 or less, or 0 or more and 6 or less, or 0 or more and 5 or less.

ここで、ｎ’は０≦ｎ’≦１０の範囲を満たす値であり、ｍ’は０≦ｍ’≦１０の範囲を満たす値であり、ＯＧはグリシジルエーテル（ｇｌｙｃｉｄｙｌ ｅｔｈｅｒ）基である。 The 4,4'-(9-fluorenylidene) diphenol-novolac resin represented by the chemical formula A is reacted with excess epichlorohydrin. The final product, an amorphous fluorene-based epoxy resin represented by the following chemical formula B, can be produced by dissolving and epoxidizing it by reaction with NaOH under reduced pressure conditions.

Here, n' is a value satisfying the range of 0≦n'≦10, m' is a value satisfying the range of 0≦m'≦10, and OG is a glycidyl ether group.

As an example, a 1 to 20-fold molar excess of epichlorohydrin, preferably a 3- to 8-fold molar excess of epichlorohydrin to the hydroxyl group of the phenolic resin, is added to the fluorene-based phenolic resin produced by the above synthesis method. It is obtained by dissolving sodium hydroxide in solid or aqueous solution and further reacting it under reduced pressure at a reaction temperature of 30° C. to 120° C. for 0.5 hours to 10 hours. At this time, the reason for conducting the reaction under reduced pressure is to remove the water generated by the reaction with sodium hydroxide or potassium hydroxide or the water used in the reaction. Epoxidation can be performed while suppressing side reactions.

Epoxy Resin Composition and Cured Product In still another embodiment of the present invention, an epoxy resin composition containing the above-mentioned amorphous fluorene-based epoxy resin and a cured epoxy resin product formed from the composition are provided.

In particular, the epoxy resin composition may be an epoxy resin curable composition containing the above-mentioned amorphous fluorene-based epoxy resin and a curing agent.

前記化学式１中、
Ｒ_１およびＲ_２はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基であり、

前記繰り返し単位１中、
ｎは２≦ｎ≦１０の範囲を満たす値であり、
Ｒ_３およびＲ_４はそれぞれ独立して、水素、置換または非置換の炭素数１～１０のアルコキシ基、置換または非置換の炭素数１～１０のアルキル基、置換または非置換の炭素数３～２０のシクロアルキル基、または置換または非置換の炭素数６～３０のアリール基である。 Specifically, it contains a fluorene-based epoxy compound represented by the following chemical formula 1 and a novolak-type fluorene-based epoxy compound containing the following repeating unit 1, and the total weight of the novolak-type fluorene-based epoxy compound containing the following repeating unit 1. An epoxy resin curable composition is provided, which is a varnish composition containing an amorphous fluorene-based epoxy resin, a curing agent, a curing catalyst, and a solvent in an amount of 3% to 80% on a basis.

In the chemical formula 1,
R ₁ and R ₂ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 10 carbon atoms; 20 cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

In the repeating unit 1,
n is a value satisfying the range of 2≦n≦10,
R ₃ and R ₄ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 10 carbon atoms; 20 cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

A detailed explanation of the chemical formula 1 and the repeating unit 1 is as described above, so the detailed explanation will be omitted here.

The epoxy resin composition contains the above-mentioned amorphous epoxy resin, thereby achieving excellent thermal stability, high flexibility and refractive index, and ensuring workability and storage stability. Semiconductor package laminates, high frequency transmission laminates, and copper clad laminates (CCL) solve the problems of fluidity and smoothness deterioration that occur when forming novolacs by adjusting the crystallinity to the optimum point. ), flexible display substrates, insulating plates, and other laminates.

Components other than the epoxy resin can be selected from those commonly known in the art.

Furthermore, the epoxy resin may further contain a non-fluorene epoxy compound that does not contain a fluorene structure, if necessary, in order to adjust the physical properties.

For example, the non-fluorene epoxy compounds include bisphenol A, bisphenol F, 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl Sulfone, 4,4'-dihydroxydiphenylketone, 4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, resorcinol, catechol, hydroquinone, dihydroxynaphthalene, etc. or allylated products of the above compounds or dihydric phenols such as allylated bisphenol A, allylated bisphenol F, and allylated novolak resin; or bisphenol A novolak, o-cresol novolak, m-cresol novolak, p- Trivalent or higher phenols such as cresol novolak, xylenol novolak, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene resin; or halogenated bisphenol such as tetrabromobisphenol A, or selected from these may be a glycidyl ether compound derived from one of the mixtures described above.

By using the amorphous fluorene epoxy resin of the present invention and the non-fluorene epoxy compound in a weight ratio of 1:3 to 3:1 or 1:2 to 2:1, shrinkage rate, elastic modulus and moldability can be improved. It is possible to achieve the unique properties of high flexibility, high refraction, and high heat resistance.

Further, the curing agent may include one selected from the group including phenol novolac resin, cresol novolak resin, dicyclopentadiene resin, and dicyandiamide, or a mixture of two or more of these. For example, the phenol novolac resin may have two or more hydroxyl groups, and the hydroxyl equivalent weight (OHEW) may be from 80 g/eq to 200 g/eq. Here, the hydroxyl group equivalent is a value obtained by dividing the number average molecular weight (g/mol) of the resin by the number of hydroxyl group equivalents (eq/mol).

In the epoxy resin composition, the composition ratio of the epoxy resin and the curing agent is determined by the number of epoxy groups in the epoxy resin relative to the hydroxyl groups in the curing agent, or the ratio of the epoxy groups in the epoxy resin to the amine active hydrogen groups in the curing agent. The molar ratio of the number of groups is preferably 0.8 to 1.2 (epoxy group/(hydroxyl group or amine active hydrogen group)).

Further, the solvent may be any one selected from the group including ketone solvents, acetate solvents, carbitol solvents, aromatic hydrocarbon solvents, and amide solvents, or two or more of these. It can be a mixture.

Examples of the ketone solvent include methyl ethyl ketone, cyclohexanone, etc. Examples of the acetate solvent include ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and examples of the carbitol solvent include: Examples of the aromatic hydrocarbon solvents include toluene and xylene, and examples of the amide solvents include dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. .

Meanwhile, the epoxy resin composition may further include a curing catalyst. At this time, the curing catalyst may be one selected from the group including imidazole compounds, phosphine compounds, phosphonium salts, and tertiary amines, or a mixture of two or more of these.

In yet another embodiment of the present invention, a cured epoxy resin product formed from the above-described epoxy resin composition is provided.

Specifically, the cured epoxy resin product may be obtained by forming the epoxy resin composition into a fully cured state or a semi-cured state, depending on the intended use or function. Since the description of the epoxy resin composition is as described above, the description will be omitted here.

In some cases, the cured epoxy resin may be in the form of a prepreg formed by drying glass fiber impregnated with the epoxy resin composition.

Laminate In yet another embodiment of the present invention, a laminate to which the epoxy resin composition is applied is provided.

Specifically, a laminate is provided that includes a substrate and a resin layer located on one or both surfaces of the substrate, and the resin layer is formed from the above-mentioned epoxy resin composition.

The resin layer may be formed by forming the epoxy resin composition in a cured or semi-cured state depending on the intended use or function. Since the description of the epoxy resin composition is as described above, the description will be omitted here.

Meanwhile, the substrate may be one selected from the group consisting of a semiconductor substrate, a copper foil plate, and an insulating plate. For example, as in Example 1-1 and the accompanying evaluation example described below, a copper foil plate can be used for the substrate, and the laminate can be realized by CCL (Copper Clad Laminate). However, this is just an example, and one embodiment of the present invention is not limited thereto.

A method for manufacturing a laminate In yet another embodiment of the present invention, the steps include: impregnating glass fibers with a composition; and drying the glass fibers impregnated with the composition to obtain a prepreg. , a method for manufacturing a laminate including the steps of laminating the prepreg on a substrate and then press-bonding the prepreg to obtain a laminate.

This is one of several ways to manufacture the laminates described above. It is possible to use only one sheet of the prepreg, or it is also possible to manufacture and use a plurality of sheets.

Furthermore, it is possible to use only one substrate, or it is also possible to use a plurality of substrates. When a plurality of substrates are used, in the step of laminating the prepregs on the substrates and then press-bonding them to obtain a laminate, the prepregs are placed between two different substrates and then press-bonded.

Regardless of the number of the prepregs and the laminates, the compression pressure, temperature, time, etc. in the step of laminating the prepregs on the substrate and then compressing them to obtain the laminates follow those generally known in the art.

Preferred embodiments are presented below to aid in understanding the invention. However, the following examples are only provided to make the present invention easier to understand, and the contents of the present invention are not limited thereby.

前記反応式１中、ｘは０≦ｘ≦１０の範囲を満たす値、つまり、ｘは０以上～１０以下、または０以上～６以下、または０以上～５以下の範囲を満たす値である。特に、ｘ＝０である場合、反応物であるモノマーを示す。 (I) Primary reaction (step 1): Production of fluorene-based biphenol resin by novolac reaction As shown in reaction formula 1 below, 4,4'-(9-fluorenylidene) diphenol (4,4'-(9-fluorenylidene) diphenol , 4'-(9-fluorenylidene) diphenol) was prepared by reacting formaldehyde with novolac in the presence of an acid catalyst.

In the reaction formula 1, x is a value satisfying the range of 0≦x≦10, that is, x is a value satisfying the range of 0 or more and 10 or less, or 0 or more and 6 or less, or 0 or more and 5 or less. In particular, when x=0, it indicates a monomer that is a reactant.

Example 1-1
First, 100 g (0.285 mol) of 4,4'-(9-fluorenylidene) diphenol and 1 g (0.011 mol) of oxalic acid dihydrate as an acid catalyst were placed in a 1 L reaction vessel. , 2-methoxyethanol) and dissolved at 80°C. Thereafter, 3.9 g (0.048 mol) of 37% (w/v) formaldehyde was added, the temperature was raised to 120° C., and the mixture was reacted for 4 hours. At this time, the 4,4'-(9-fluorenylidene) diphenol compound and formaldehyde were reacted at a molar ratio of 6:1, and oxalic acid was reacted with 100 moles of the 4,4'-(9-fluorenylidene) diphenol compound. The reaction was carried out at 3.86 mol based on . Methyl cellosolve was recovered at normal pressure (25°C) while increasing the temperature to 180°C, and further vacuum recovery was performed to 20 torr or less. The resin from which solvent recovery was completed was solidified at room temperature, and the softening point of Example 1-1 was 135°C.

Example 2-1
In a 1 L reaction vessel, 100 g (0.285 mol) of 4,4'-(9-fluorenylidene) diphenol and 1 g (0.285 mol) of oxalic acid as an acid catalyst were added. 011 mol) was added to 200 g of methyl cellosolve (2-methoxyethanol) and dissolved at 80°C. Thereafter, 2.9 g (0.036 mol) of 37% formaldehyde was added, the temperature was raised to 120° C., and the mixture was reacted for 4 hours. At this time, the 4,4'-(9-fluorenylidene) diphenol compound and formaldehyde were reacted at a molar ratio of 8:1, and oxalic acid was reacted with 100 moles of the 4,4'-(9-fluorenylidene) diphenol compound. The reaction was carried out at 3.86 mol based on . After the reaction was completed, methyl cellosolve was recovered at normal pressure (25°C) while increasing the temperature to 180°C, and further vacuum recovery was performed to 20 torr or less. The resin from which the solvent was recovered was solidified at room temperature, and the softening point of Example 2-1 was 127°C.

Comparative example 1-1
Crystallization characteristics were evaluated using a 99.9% pure monomer that does not undergo a novolac reaction with a 4,4'-(9-fluorenylidene) diphenol compound as a comparison group.

Comparative example 2-1
The molar ratio of the 4,4'-(9-fluorenylidene) diphenol compound and formaldehyde is 0.55:1, and the oxalic acid is The reaction proceeded under the same conditions as in Example 1, except that the reaction was carried out at 9.8 mol. The produced resin exhibited amorphous characteristics at room temperature and had a softening point of 197°C.

The 4,4'-(9-fluorenylidene) diphenol-novolak resins of Examples 1-1 to 2-1 and Comparative Examples 1-1 to 2-1 ) diphenol-novolac resin), specific reaction molar ratio conditions and results of physical property measurements for the resin are shown in Table 1 below.

In particular, in evaluating the crystallinity of resins, melting point (Tm, °C), hydroxyl equivalent (OHEW, g/eq), and softening point (°C) are measured, and number average molecular weight (Mn, g/mol), and weight average molecular weight (Mw, g/mol), molecular weight distribution (Mn/Mw), content of the monomer compound represented by the chemical formula 1 (monomer content of n=1, %), and the repeating unit 1. The novolac polymer (polymer content with n=2 or more, %) was measured. At this time, the value is measured based on the total weight of the monomer compound represented by the chemical formula 1 and the novolac polymer containing the repeating unit 1 (polymer content of n=2 or more, %).

At this time, the physical properties were measured using differential scanning calorimetry (DSC) and gel permeation chromatography (GPC), respectively, and the specific measurement methods were as described above.

On the other hand, differential scanning calorimetry (DSC) analysis graphs for the fluorene biphenol resin of Example 1-1 and the 4,4'-(9-fluorenylidene) diphenol compound of Comparative Example 1-1 are shown in the figures. 1 and FIG. 2.

In particular, as shown in Figure 1, the DSC curve of Example 1-1 shows that the resin was manufactured using a fluorene-based biphenol resin containing a novolac-type compound made by bonding monomers together and formed with a compound bond with a large molecular weight, and as an amorphous solid. No melting point appeared, and as shown in FIG. 2, the DSC curve of Comparative Example 1-1 showed that the melting point was 232° C., which is a characteristic of a crystalline resin having a monomer structure.

In addition, analysis graphs of gel permeation chromatography (GPC) for the fluorene biphenol resin of Example 1-1 and the 4,4'-(9-fluorenylidene) diphenol compound of Comparative Example 1-1 are shown in the figures. 3 and FIG. 4.

In particular, as shown in Figure 3, the GPC curve of Example 1-1 confirms the molecular weight distribution map of the fluorene-based biphenol resin that contains a compound with a novolac type structure having a repeating unit of n = 2 or 3 or more. As shown in FIG. 4, the GPC curve of Comparative Example 1-1 shows that 4,4'-(9-fluorenylidene) diphenol compound has a monomer or monomer structure having repeating unit n=1. We were able to confirm that it appeared as a single peak.

On the other hand, as shown in Table 1 above, as a result of checking the molecular weight distribution of Example 1-1, Example 2-1, and Comparative Example 2-1, it was confirmed that a polymer larger than a dimer was synthesized. It was confirmed that the crystallinity was sufficiently controlled by measuring the melting point (Tm) using a differential scanning calorimeter (DSC).

(II) Secondary reaction (step 2): Production of the final substance by epoxidation reaction As shown in reaction formula 2 below, the 4,4'-(9-fluorenylidene) diphenol-novolac resin (4 , 4'-(9-Fluorenylidene) diphenol-novolac resin) was reacted with epihalohydrin in the presence of a hydroxide salt to prepare an amorphous fluorene-based epoxy resin as a final material.

In Reaction Formula 2, x is a value satisfying the range of 0≦x≦10, y is a value satisfying the range of 0≦y≦10, and OG is a glycidyl ether group. Specifically, x and y each have a value satisfying a range of 0 or more and 10 or less, 0 or more and 6 or less, or 0 or more and 5 or less. In particular, when x=0 and y=0, the monomers corresponding to the respective reactants are indicated.

Example 1-2
In a 1 L reaction vessel, add 100 g (0.53 mol) of the 4,4'-(9-fluorenylidene) diphenol-novolac resin of Example 1-1 to 296 g (3.2 mol) of epichlorohydrin. and dissolved at 65°C. Thereafter, 42 g (0.525 mol) of 50% NaOH was added dropwise to react at 30° C. to 80° C. for 4 hours under a reduced pressure of 180 torr. At this time, the epichlorohydrin is reacted with the hydroxyl group of the 4,4'-(9-fluorenylidene) diphenol-novolac resin at a molar content of 3 to 8 times, and NaOH is 0.85 times the molar content. The reaction was carried out at ~1.2 times the molar content. The pressure was maintained at 180 torr, and the reaction proceeded at 30° C. to 120° C. During the reaction process, water was continuously removed to suppress side reactions caused by water. After the reaction was completed, generated salts and side reactants were removed using methyl isobutyl ketone (MIBK), toluene, and distilled water. The epoxy equivalent of the amorphous fluorene-based epoxy resin thus produced was 250 g/eq.

As a result of confirming the molecular weight distribution of the product of Example 1-2 produced in this way by GPC analysis, a polymer larger than a dimer was synthesized, and the secondary reaction product after the epoxidation reaction was Ball and Ring. The softening point was determined by the method.

Example 2-2
The epoxidation reaction was carried out in the same manner as the secondary reaction conditions of Example 1-2, except that 100 g of the 4,4'-(9-fluorenylidene) diphenol-novolak resin of Example 2-1 was used. did.

As a result of confirming the molecular weight distribution of the product of Example 2-2 produced in this way by GPC analysis, a polymer larger than a dimer was synthesized, and the secondary reaction product after the epoxidation reaction was Ball and Ring. The softening point was determined by the method.

Comparative example 1-2
An epoxy resin was produced in the same manner as in Example 1-1, except that the 99.9% pure 4,4'-(9-fluorenylidene) diphenol compound of Comparative Example 1-1 was used.

Comparative example 2-2
100 g (0.52 mol) of the 4,4'-(9-fluorenylidene) diphenol-novolak resin of Comparative Example 2-1 was added to 296 g (3.2 mol) of epichlorohydrin, and dissolved at 65°C. Ta. Then, 42 g (0.525 mol) of 50% NaOH was added dropwise to react at 30°C to 80°C for 4 hours under a reduced pressure of 180 torr, and after the reaction was completed, methyl isobutyl ketone (MIBK), Generated salts and side reactants were removed using toluene and distilled water.

As a result of confirming the molecular weight distribution of the product of Comparative Example 2-2 produced in this way by GPC analysis, a polymer larger than a dimer was synthesized, and the secondary reaction product after the epoxidation reaction was Ball and Ring. The softening point was determined by the method.

前記構造式中、ｚは１≦ｚ≦１０の範囲を満たす値である。 Comparative example 3-2
A commercially available phenol novolac epoxy resin (trade name: YDPN-638EK80, manufactured by Kokuto Kagaku Co., Ltd., EEW 179.7 g/eq, viscosity 370 cps @ 25 ° C.) was used, and the structural formula of the epoxy resin (YDPN-638EK80) was as follows. be.

In the above structural formula, z is a value satisfying the range of 1≦z≦10.

The melting points (Tm, °C) measured for the evaluation of resin crystallinity for the fluorene-based epoxy resins of Examples 1-2 to 2-2 and Comparative Examples 1-2 to 2-2, and Epoxy equivalent weight (EEW, g/eq), softening point (Ts, °C), number average molecular weight (Mn, g/mol) by GPC analysis, weight average molecular weight (Mw, g/mol), molecular weight distribution (Mn/Mw ), melt viscosity (cps@150°C), storage stability (50% dilution with cyclohexanone), and refractive index (R.I) are as shown in Table 2 below.

At this time, the physical properties were measured using differential scanning calorimetry (DSC) and gel permeation chromatography (GPC), respectively, and the specific measurement methods were as described above.

However, the melt viscosity of the fluorene-based epoxy resin was measured at 150°C using a rotational viscometer manufactured by Brookfield, and the storage stability was determined by dissolving the sample in cyclohexanone solvent at a weight ratio of 1:1. After that, the phenomenon of crystallization and precipitation at room temperature (RT, 23°C to 25°C) was measured, and the refractive index (R. It was measured.

As shown in Table 2 above, the amorphous fluorene-based epoxy resins of Examples 1-2 and 2-2 lowered the crystallinity while at the same time, the softening point and melt viscosity of Comparative Example 2-2 increased. lower than epoxy resin. This is a solidified resin that can be applied to a variety of fields such as electronic materials that require high functionality, while maintaining the unique characteristics of the fluorene structure such as high refractive index with minimal deformation. Manufactured.

<Test example>
Copper clad laminates (CCL) were applied to the epoxy resins of Examples 1-2 to 2-2, Comparative Examples 1-2, 2-2, and 3-2 in the following manner. The physical properties of the clad laminate were measured during production, and the measurement results are shown in Table 3 below.

1) Manufacture of test pieces for CCL evaluation Each epoxy resin, curing agent, and curing catalyst of Examples and Comparative Examples were mixed at a composition of 32% by weight and 0.02% by weight, respectively, based on the total weight of solid content. A varnish solution having a solid content of 70% by weight was prepared using methyl ethyl ketone (MEK) as a solvent. Here, a phenol novolac curing agent having a softening point of 95.2° C. was used as the curing agent, and 2-methylimidazole (2MI, 2-methylimidazole) was used as the catalyst. The solution viscosity of the thus produced varnish solution was measured at 25° C. using a rotational viscometer manufactured by Brookfield, and the measurement results are shown in Table 3 below.

2116 type E-glass glass fibers were impregnated with each of the varnish solutions prepared as above, and then dried in an oven at 175° C. for 2 minutes to prepare respective prepregs.

Eight sheets of each prepreg were placed between two sheets of 1 oz copper foil and then hot pressed at a temperature of 180° C. and a pressure of 200 psi for 1 hour and 30 minutes to form each prepreg. A test piece for evaluating CCL physical properties was obtained.

2) Glass transition temperature (Tg)
The glass transition temperature (Tg) was determined by IPC TM-650 2.4.25 using a differential scanning calorimeter (DSC) after curing the resin compositions of each example and comparative example at 180°C for 6 hours. Measured according to the standard.

3) Coefficients of thermal expansion (CTE)
The coefficient of thermal expansion (CTE) was measured according to the IPC TM-650 2.4.24 standard after curing the resin compositions of each example and comparative example at 180° C. for 6 hours.

4) Flexural modulus
The flexural modulus of elasticity was determined by manufacturing resin-coated metal foils by attaching the resin compositions of each example and comparative example to metal foil, and measuring two sheets of each resin-coated metal foil facing the resin surface. By overlapping, a double-sided copper-clad laminate was produced. After etching the entire surface of each double-sided copper clad laminate, it was cut into 5 mm width x 30 mm length and calculated using DMA (Dynamic Mechanical Analysis).

Claims (14)

Contains a fluorene-based epoxy compound represented by the following chemical formula 1 and a novolak-type fluorene-based epoxy compound containing the following repeating unit 1, and 3% of the novolak-type fluorene-based epoxy compound containing the following repeating unit 1 based on the total weight. ~ 30% amorphous fluorene epoxy resin:

In the chemical formula 1,
R ₁ and R ₂ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 10 carbon atoms; 20 cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

In the repeating unit 1,
n is a value satisfying the range of 2≦n≦10,
R ₃ and R ₄ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 10 carbon atoms; 20 cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. The amorphous fluorene according to claim 1, wherein the fluorene-based epoxy compound represented by the chemical formula 1 and the novolac-type fluorene-based epoxy compound containing the repeating unit 1 are contained in a weight ratio of 97:3 to 70:30 . epoxy resin. The amorphous fluorene system according to claim 1, wherein R ₁ and R ₂ in the chemical formula 1 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Epoxy resin. The melting point is 30°C to 68°C,
The number average molecular weight is 200 g/mol to 2000 g/mol,
The amorphous fluorene-based epoxy resin according to claim 1, having an epoxy equivalent of 200 g/eq to 500 g/eq. In the presence of an acid catalyst, a fluorene-based biphenol compound represented by the following chemical formula 2 and formaldehyde are reacted at a molar ratio of 2.5:1 to 10:1 to produce a novolak-type fluorene-based biphenol compound containing the following repeating unit 2. a step of producing a fluorene-based biphenol resin containing;
A method for producing an amorphous fluorene-based epoxy resin, comprising the step of reacting the fluorene-based biphenol resin with epihalohydrin in the presence of a hydroxide salt:

In the chemical formula 2,
R ₅ and R ₆ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 10 carbon atoms; 20 cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

In the repeating unit 2,
m is a value satisfying the range of 2≦m≦10,
R ₇ and R ₈ are each independently hydrogen, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 3 to 10 carbon atoms; 20 cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. The method for producing an amorphous fluorene-based epoxy resin according to claim 5, wherein the fluorene-based biphenol compound represented by Chemical Formula 2 and formaldehyde are reacted at a molar ratio of 3:1 to 9:1. The method according to claim 5, wherein the step of reacting the fluorene-based biphenol compound represented by Formula 2 with formaldehyde is performed at 100° C. to 140° C. under conditions of 750 Torr to 770 Torr (99.9918 kPa to 102.6582 kPa). A method for producing crystalline fluorene-based epoxy resin. The amorphous fluorene system according to claim 5, wherein R ₅ and R ₆ in the chemical formula 2 are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Method of manufacturing epoxy resin. The amorphous fluorene-based epoxy according to claim 5, wherein the acid catalyst is one or more selected from the group consisting of oxalic acid, sulfuric acid, hydrochloric acid, phosphoric acid, para-toluenesulfonic acid, methylsulfonic acid, and acetic acid. Method of manufacturing resin. The amorphous fluorene-based epoxy according to claim 5, wherein the acid catalyst is used in a content of 0.01 to 10 moles based on 100 moles of the fluorene-based biphenol compound represented by the chemical formula 2. Method of manufacturing resin. The amorphous according to claim 5, wherein the fluorene-based biphenol resin has no melting point (Tm), a number average molecular weight of 200 g/mol to 2000 g/mol, and a hydroxyl equivalent of 175 g/eq to 250 g/eq. A method for producing a fluorene-based epoxy resin. The step of reacting the fluorene-based biphenol resin with epihalohydrin is performed at 25° C. to 120° C. under pressure conditions of 100 Torr to 300 Torr (13.3322 kPa to 39.9967 kPa) in the presence of a hydroxide salt. A method for producing amorphous fluorene-based epoxy resin. An epoxy resin composition comprising the amorphous fluorene-based epoxy resin according to claim 1, a curing agent, a curing catalyst, and a solvent. A substrate and
a resin layer located on one or both sides of the substrate,
A laminate, wherein the resin layer is formed from the epoxy resin composition according to claim 13.

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