Preparation method of dicyclopentadiene-based epoxy resins

Abstract

The present invention provides a method for effectively preparing dicyclopentadiene-based epoxy resins in an environmentally-friendly manner without using a phenol-based compound.

Description

Method for producing dicyclopentadiene-based epoxy resin

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2023-0117871, filed September 5, 2023, and Korean Patent Application No. 10-2024-0120884, filed September 5, 2024, the entire contents of which are incorporated herein by reference.

[0003]

[0004] The present invention relates to a method for producing a dicyclopentadiene-based epoxy resin having a high epoxy content in an environmentally friendly manner without using a phenol-based compound.

[0005]

[0006] Recently, with the miniaturization of mobile communication devices, satellite broadcasting receivers, computers, etc., the electronic components used in these devices are also becoming miniaturized, complex, highly functional, and highly precise. In addition, there is a demand for high-density and high-speed signal transmission response in the wiring patterns of the internal substrates of electronic circuit components.

[0007]

[0008] Furthermore, the frequency band of signals used in electronic communication devices is transitioning from the MHz range to the GHz range. As the frequency of electrical signals increases, transmission loss increases, so the development of electrical insulating materials with excellent high-frequency transmission characteristics and substrates using such materials is essential. Accordingly, to respond to the recent trend toward high-performance electronic devices, there is a demand for copper clad laminate (CCL) substrates with low dielectric constant and low dielectric loss factor in the GHz range, resulting in excellent transmission characteristics. Organic materials with low dielectric constants include epoxy resin, Teflon resin, and polyphenylene ether (PPE), among which Teflon material is known to exhibit the best dielectric properties.

[0009]

[0010] However, in the case of Teflon, there is a disadvantage in that the adhesive properties required for IC substrates, PCBs, flexible display substrates, etc. are significantly poor, and in the case of cyanate resin, high energy is required for curing at a temperature of 230℃, and it is easily gelled in alcoholic hydroxyl such as moisture, so its use is limited. In addition, in the case of polyphenylene ether, it is simply added in a non-reactive form, causing problems such as a decline in adhesive properties and unevenness of the adhesive layer surface on the curing matrix of the adhesive layer for IC substrates, PCBs, flexible display substrates, etc.

[0011]

[0012] For this reason, epoxy resins, which have high adhesive properties, low permittivity, low dielectric loss, and are easy to use, are increasingly being used as materials for CCLs. However, epoxy resins also have the disadvantage of being disadvantageous in controlling the propagation speed and impedance of signals in the high-frequency range. To improve these disadvantages, a method of blending epoxidized polyphenylene oxide resins with epoxy resins has been proposed. However, when polyphenylene oxide is used, it has been pointed out that the adhesiveness and heat resistance are lowered, and the curing properties with epoxy resins are poor.

[0013]

[0014] Furthermore, a method for manufacturing such curable epoxy resins involves reacting petroleum resins such as phenol with the resin and then epoxidizing the resulting epoxy resin. However, this manufacturing process involves the use of highly toxic substances such as phenol, and requires a post-processing step to separate and purify the resin using organic solvents and water.

[0015]

[0016] Accordingly, there is a need for the development of a novel manufacturing method that can provide a reactive dicyclopentadiene-based epoxy resin with a high epoxy content and excellent hydrophobic and low viscosity characteristics that can be used in various fields such as IC substrates, PCBs, and flexible display substrates, through an environmentally friendly process that does not use phenol, etc.

[0017]

[0018] [Prior Art Literature]

[0019] [Patent Document]

[0020] Republic of Korea Patent Publication No. 10-2015-0078859

[0021]

[0022] The present invention aims to provide a method for producing a dicyclopentadiene-based epoxy resin having a high epoxy content in an environmentally friendly manner without using a phenol-based compound.

[0023]

[0024] In addition, the present invention seeks to provide a dicyclopentadiene-based epoxy resin manufactured by the above-described method.

[0025]

[0026] According to one embodiment of the present invention, there is provided a step of first thermal polymerization of a monomer mixture comprising an epoxy monomer and a dicyclopentadiene monomer; and

[0027] A step of subjecting the product obtained through the first thermal polymerization reaction to a second thermal polymerization reaction;

[0028] Including,

[0029] The monomer mixture comprises 10 to 60 wt% of the epoxy monomer and 90 to 40 wt% of the dicyclopentadiene monomer within 100 wt% of the total mixture.

[0030] A method for producing a dicyclopentadiene-based epoxy resin is provided.

[0031]

[0032] According to another embodiment of the present invention, a dicyclopentadiene-based epoxy resin manufactured by the above-described method is provided.

[0033]

[0034] According to the present invention, a dicyclopentadiene-based epoxy resin having a high epoxy content can be effectively manufactured in an environmentally friendly manner without using a phenol-based compound.

[0035]

[0036] Figures 1 to 4 are measurements taken for each of the dicyclopentadiene-based epoxy resins synthesized according to Examples 1 to 4 as an embodiment of the present invention. 1 This shows the H-NMR analysis graph.

[0037]

[0038] Figure 5 is a measurement result for the dicyclopentadiene-based fully hydrogenated resin (HC-100, Hanwha Solutions petroleum resin commercial product) of Comparative Example 1. 1 This shows the H-NMR analysis graph.

[0039]

[0040] FIGS. 6 to 9 illustrate differential scanning calorimetry (DSC) analysis graphs measured after curing each of the dicyclopentadiene-based epoxy resins synthesized according to Examples 1 to 4 as an embodiment of the present invention.

[0041]

[0042] Figures 10 and 11 show differential scanning calorimetry (DSC) analysis graphs measured after curing the bisphenol A type epoxy resin of Comparative Example 2 and the phenol novolac resin of Comparative Example 3, respectively.

[0043]

[0044] 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.

[0045]

[0046] Furthermore, the terminology used herein is merely for the purpose of describing exemplary embodiments and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprise," "include," or "have" indicate the presence of a feature, number, step, component, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0047]

[0048] The terms "about," "substantially," and the like used throughout this specification are used to mean at or near the numerical value when manufacturing and material tolerances inherent to the meanings stated are presented, and are used to prevent unscrupulous infringers from unfairly exploiting disclosures that state precise or absolute values ​​to aid understanding of this specification. The terms "step of doing" or "step of" used throughout this specification do not mean "step for doing."

[0049]

[0050] In this specification, the term "combination of these" included in the expression in the Makushi format means one or more mixtures or combinations selected from the group consisting of the components described in the expression in the Makushi format, and means including one or more selected from the group consisting of the components.

[0051]

[0052] In this specification, and means a bond that connects to another substituent.

[0053]

[0054] The present invention is susceptible to various modifications and takes various forms. Specific embodiments are illustrated and described in detail below. However, this is not intended to limit the present invention to specific disclosed forms, but rather to encompass all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0055]

[0056] Based on the above definitions, implementation examples of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention. The present invention is defined solely by the scope of the claims set forth below.

[0057]

[0058] Method for producing dicyclopentadiene-based epoxy resin

[0059] In one embodiment of the invention, a method for effectively producing a dicyclopentadiene-based epoxy resin in an environmentally friendly manner without using a phenol-based compound is provided.

[0060]

[0061] Specifically, the method for producing a dicyclopentadiene-based epoxy resin according to the present invention is characterized by performing a second thermal polymerization after performing a first thermal polymerization as follows, and includes a step of performing a first thermal polymerization reaction on a monomer mixture including an epoxy-based monomer and a dicyclopentadiene-based monomer; and a step of performing a second thermal polymerization reaction on a product obtained through the first thermal polymerization reaction.

[0062]

[0063] In particular, the monomer mixture includes 10 wt% or more and 60 wt% or less of the epoxy monomer and 90 wt% or less and 40 wt% or more of the dicyclopentadiene monomer within 100 wt% of the total mixture.

[0064]

[0065] Specifically, the epoxy monomer may be included in an amount of 15 wt% or more, or 20 wt% or more, or 25 wt% or more, or 30 wt% or more, or 35 wt% or more, or 40 wt% or more, or 45 wt% or more, or 50 wt% or more, but not more than 60 wt%, or not more than 58 wt%, or not more than 56 wt%, or not more than 55 wt%.

[0066]

[0067] In addition, the dicyclopentadiene monomer may be included in an amount of 85 wt% or less, or 80 wt% or less, or 75 wt% or less, or 70 wt% or less, or 65 wt% or less, or 60 wt% or less, or 55 wt% or less, or 50 wt% or less, but 40 wt% or more, or 42 wt% or more, or 44 wt% or more, or 45 wt% or more.

[0068]

[0069] Specifically, the epoxy monomer may be a compound containing an allyl group together with an epoxy group and having 1 to 18 carbon atoms, and preferably a compound containing 1 to 15 carbon atoms, or 1 to 12 carbon atoms, or 1 to 10 carbon atoms, or 1 to 8 carbon atoms, or 1 to 7 carbon atoms.

[0070]

[0071] In addition, the epoxy monomer may be a compound that includes an allyl group together with an epoxy group and further includes an ether group [-(C=O)-] and an ester group [-(OC=O)-].

[0072]

[0073] Meanwhile, the epoxy monomer may be represented by any one of the following structural formulas.

[0074] .

[0075]

[0076] For example, the epoxy monomer may be at least one selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, ethyl glycidyl acrylate, ethyl glycidyl methacrylate, propyl glycidyl acrylate, propyl glycidyl methacrylate, butyl glycidyl acrylate, butyl glycidyl methacrylate, 3,4-epoxy-butyl methacrylate, 6,7-epoxy-heptyl methacrylate, 3,4-epoxy-cyclohexyl methyl methacrylate, 3,4-epoxy-cyclohexyl-methyl methacrylate, 4-vinyl cyclohexene oxide, o-vinyl benzene glycidyl ether, m-vinyl benzene glycidyl ether, and p-vinyl benzene glycidyl ether.

[0077]

[0078] More specifically, the epoxy monomer may have the following structural formula.

[0079] .

[0080]

[0081] Additionally, the dicyclopentadiene monomer may be dicyclopentadiene.

[0082]

[0083] Specifically, the dicyclopentadiene monomer may have the following structural formula.

[0084] .

[0085]

[0086] Additionally, the monomer mixture may contain 30% or more and 60% or less of the dicyclopentadiene monomer based on the weight of the epoxy monomer.

[0087]

[0088] Meanwhile, the first thermal polymerization reaction can be performed under conditions of 255°C or higher and 285°C or lower.

[0089]

[0090] Specifically, the first thermal polymerization reaction may be performed under conditions of a temperature of 260°C to 270°C, or a temperature of 262°C to 268°C, or a temperature of 264°C to 266°C, and a pressure of 20 bar to 30 bar, or a pressure of 23 bar to 28 bar, or a pressure of 24 bar to 27 bar. At this time, the reaction time may be 30 minutes to 50 minutes, or 32 minutes to 45 minutes, or 33 minutes to 44 minutes, or 34 minutes to 43 minutes, or 35 minutes to 42 minutes.

[0091]

[0092] The above primary thermal polymerization reaction can be performed using a continuous stirred-tank reactor (CSTR).

[0093]

[0094] Meanwhile, the secondary thermal polymerization reaction can be performed under conditions of 255°C or higher and 285°C or lower.

[0095]

[0096] Specifically, the secondary thermal polymerization reaction may be performed under conditions of a temperature of 260°C to 270°C, or a temperature of 262°C to 268°C, or a temperature of 264°C to 266°C, and a pressure of 20 bar to 30 bar, or a pressure of 23 bar to 28 bar, or a pressure of 24 bar to 27 bar. At this time, the reaction time may be 40 minutes to 80 minutes, or 45 minutes to 75 minutes, or 50 minutes to 70 minutes, or 55 minutes to 68 minutes, or 60 minutes to 67 minutes.

[0097]

[0098] The above secondary thermal polymerization reaction can be performed using a continuous flow reactor (PFR; Plug flow reactor).

[0099]

[0100] Dicyclopentadiene-based epoxy resin

[0101] In another embodiment of the present invention, a dicyclopentadiene-based epoxy resin manufactured by the method described above is provided.

[0102]

[0103] Specifically, the core structure of the above dicyclopentadiene-based epoxy resin is characterized by being formed by directly thermally polymerizing an epoxy monomer and a dicyclopentadiene-based monomer in an environmentally friendly manner that does not use a phenol-based compound.

[0104]

[0105] In addition, the above dicyclopentadiene-based epoxy resin, 1 In H-NMR analysis, it may have a double peak with a first peak at 3.5 ppm to 4.2 ppm and a second peak at 4.3 ppm to 4.8 ppm. The specific measurement method is as shown in Test Example 1 below.

[0106]

[0107] Also, the area ratio of the above double peaks is 1 In H-NMR analysis, the area of ​​the entire graph may be 8% to 60%, preferably 9% to 58%, or 9.4% to 56%.

[0108]

[0109] At this time, the double peak may have an area ratio of 90% or more and 110% or less of the first peak and the second peak, and may have substantially the same area.

[0110]

[0111] Meanwhile, the dicyclopentadiene-based epoxy resin may have a weight average molecular weight (Mw) measured by GPC analysis of 500 g / mol or more to 1000 g / mol or less, or 550 g / mol or more to 900 g / mol or less, or 600 g / mol or more to 800 g / mol or less. A specific measurement method is as shown in Test Example 1 below.

[0112]

[0113] In addition, the dicyclopentadiene-based epoxy resin may have a number average molecular weight (Mn) measured by GPC analysis of 200 g / mol or more to 700 g / mol or less, or 250 g / mol or more to 650 g / mol or less, or 300 g / mol or more to 600 g / mol or less. A specific measurement method is as shown in Test Example 1 below.

[0114]

[0115] In addition, the dicyclopentadiene-based epoxy resin may have a molecular weight distribution (PDI, Mw / Mn) of 1 or more and 2 or less, or 1.2 or more and 1.9 or less, or 1.5 or more and 1.7 or less.

[0116]

[0117] Specifically, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (PDI, Mw / Mn) of the dicyclopentadiene-based epoxy resin can be measured using gel permeation chromatography (GPC, Infinity1260). For example, the dicyclopentadiene-based epoxy resin is dissolved in tetrahydrofuran to a concentration of 5 wt%, 10 μL is injected into GPC, tetrahydrofuran is used as the mobile phase of GPC, and the solution is introduced at a flow rate of 1 mL / min, and the analysis can be performed at 35°C. At this time, one Guard column and three PL gels 5 μm 500A, PL gel 5 μm 100A, and PL gel 5 μm 50A are connected in series, and a refractive index detector (RID) is used as the detector to measure at 35°C. The values ​​of Mw and Mn can be derived using a calibration curve formed using polystyrene standard specimens.

[0118]

[0119] In addition, the dicyclopentadiene-based epoxy resin may have an epoxy equivalent of 200 to 1500 g / eq, or 200 to 1480 g / eq, or 250 to 1450 g / eq, as measured according to the JIS K 7236 standard. A specific measurement method is as shown in Test Example 1 below.

[0120]

[0121] Meanwhile, the above dicyclopentadiene-based epoxy resin has high flexibility due to the inclusion of a repeating unit derived from an epoxy monomer in the polymer structure, and accordingly exhibits a liquid state in the range of room temperature and pressure, and thus has the characteristic of having no softening point and making it difficult to directly measure the glass transition temperature (Tg).

[0122]

[0123] Accordingly, the glass transition temperature (Tg) of the dicyclopentadiene-based epoxy resin can be measured after curing, and the glass transition temperature (Tg) of the dicyclopentadiene-based epoxy resin after curing can be 55°C or more and 120°C or less. Preferably, the glass transition temperature (Tg) after the curing may be 55.5°C or higher, or 55.8°C or higher, or 56°C or higher, or 56.2°C or higher, or 56.5°C or higher, or 57°C or higher, or 60°C or higher, or 62°C or higher, or 65°C or higher, or 68°C or higher, or 70°C or higher, or 75°C or higher, or 78°C or higher, or 80°C or higher, or 85°C or higher, or 88°C or higher, or 90°C or higher, or 92°C or higher, and 115°C or lower, or 110°C or lower, or 105°C or lower. The glass transition temperature (Tg) after curing of the above dicyclopentadiene-based epoxy resin can have the above-described range in terms of simultaneously implementing high heat resistance and low viscosity characteristics with excellent thermal stability along with excellent hydrophobicity.

[0124]

[0125] The glass transition temperature (Tg) of the above dicyclopentadiene-based epoxy resin after curing can be measured using a differential scanning calorimeter (DSC). More specifically, the curing method of the above dicyclopentadiene-based epoxy resin and the method for measuring the glass transition temperature (Tg) after curing will be described in detail in the contents of Test Example 1 described below.

[0126]

[0127] For example, the temperature was increased from 25 ℃ to 200 ℃ at 10 ℃ / min using a Differential Scanning Calorimeter (DSC, TA2000) from TA Instruments (New Castle, Delaware, USA), maintained at this temperature for 1 min, and then decreased from 200 ℃ to 25 ℃ at 10 ℃ / min and maintained for 1 min. The melting temperature, melting point (Tm, ℃) can be measured while increasing the temperature again from 25 ℃ to 200 ℃ at 10 ℃ / min (2nd cycle).

[0128]

[0129] <Conditions for measuring glass transition temperature>

[0130] - DSC device: Differential Scanning Calorimeter (DSC, device name: DSC Q20, manufacturer: TA instrument)

[0131] - heating rate: 10 ℃ / min

[0132] - Cooling rate: 100 ℃ / min

[0133] - temperature program: 1st and 2nd run

[0134] - temperature range: 25-200 ℃

[0135] - 2ndrun is used to measure the Tg of materials

[0136]

[0137] <Curing conditions for resin>

[0138] - Type of hardener: Polyetheramine (curing agent) Huntsman D-230

[0139] - Hardener dosage (phr) = (AHEW / EEW)*100

[0140] AHEW (Active Hydrogen Equivalent Weight of Amine): Molecular Weight of Amine / Number of Active Hydrogens of Amine (D-230, 60g / eq)

[0141] EEW (Epoxy Equivalent Weight): Weight of epoxy resin containing 1 equivalent of epoxy group

[0142] Add the amount of hardener corresponding to the equivalent ratio based on 100g of DCPD epoxy resin.

[0143] - Curing conditions: 1 hour at 80 degrees in a vacuum oven, then 2 hours of curing after heating to 120 degrees (total 3 hours)

[0144] The hardener and the main agent (DCPD epoxy) were mixed using a Planetary Centrifugal Mixer at 2000 rpm for 5 minutes.

[0145]

[0146] Meanwhile, the dicyclopentadiene-based epoxy resin includes a “hydrophobic polymer fraction having a structure in which two or more aliphatic or aromatic rings each having 5 to 60 carbon atoms are directly bonded to each other, bonded to each other through methylene, or condensed with each other” among the molecular structures of the resin, and exhibits excellent heat stability, high heat resistance, low viscosity, and excellent hydrophobicity at the same time, and can be effectively used in various fields such as IC substrates, PCBs, and flexible display substrates.

[0147]

[0148] For example, the hydrophobic polymer fraction refers to a molecular structure capable of implementing a hydrophobic surface having a contact angle of 90 degrees or more with respect to water, by having a structure in which two or more aliphatic or aromatic rings having 5 to 60 carbon atoms, such as dicyclopentadiene or phenol, are directly bonded to each other, bonded to each other through methylene, or condensed with each other.

[0149]

[0150] In addition, the dicyclopentadiene-based epoxy resin has a low viscosity due to the polymer structural characteristics described above, and specifically, the viscosity measured at 60°C according to ASTM D 3236 may be 120,000 cps or less, or 500 cps or more and 120,000 cps or less.

[0151]

[0152] More specifically, the dicyclopentadiene-based epoxy resin has a viscosity measured at 60° C. of 119800 cps or less, or 119500 cps or less, or 119000 cps or less, or 118000 cps or less, or 115000 cps or less, or 113000 cps or less, or 110000 cps or less, or 105000 cps or less, or 100000 cps or less, or 98000 cps or less, or 95000 cps or less, or 90000 cps or less, or 75000 cps or less, or 50000 cps or less, or 35000 cps or less, or 30000 cps or less, or 25000 cps or less, or 20000 cps, as measured according to the ASTM D 3236 standard. or less, or 18000 cps or less, or 16000 cps or less, or 15500 cps or less, or 12000 cps or less, or 10000 cps or less, or 8000 cps or less, or 6000 cps or less, or 5000 cps or less, or 4500 cps or less, or 3000 cps or less, or 2000 cps or less, and also may be 520 cps or more, or 550 cps or more, or 580 cps or more, or 600 cps or more.

[0153]

[0154] In addition, the dicyclopentadiene-based epoxy resin may have a viscosity measured at 90° C. of 3000 cps or less, or 30 cps or more and 3000 cps or less, according to ASTM D 3236, and more specifically, 2800 cps or less, or 2500 cps or less, or 2200 cps or less, or 2000 cps or less, or 1950 cps or less, or 1900 cps or less, or 1750 cps or less, or 1500 cps or less, or 1300 cps or less, or 1150 cps or less, or 1100 cps or less, or 1000 cps or less, or 800 cps or less, or 750 cps or less, or 700 cps or less, or 650 cps or less, or 620 cps or less, or 600 cps or less, or It may be 580 cps or less, or 550 cps or less, or 500 cps or less, or 450 cps or less, or 400 cps or less, or 350 cps or less, or 300 cps or less, or 250 cps or less, or 200 cps or less, or 150 cps or less, or 100 cps or less, and may also be 35 cps or more, or 40 cps or more, or 45 cps or more, or 50 cps or more.

[0155]

[0156] In addition, the dicyclopentadiene-based epoxy resin may have a viscosity of 1000 cps or less, or 5 cps or more and 1000 cps or less, as measured at 190°C according to ASTM D 3236, and more specifically, 850 cps or less, or 800 cps or less, or 750 cps or less, or 700 cps or less, or 650 cps or less, or 600 cps or less, or 550 cps or less, or 500 cps or less, or 450 cps or less, or 400 cps or less, or 350 cps or less, or 300 cps or less, or 250 cps or less, or 240 cps or less, or 225 cps or less, or 200 cps or less, or 185 cps or less, or 160 cps or less, or 155 cps or less, or 150 cps or less, or 140 cps or less, or 130 cps or less, or 120 cps or less, or 110 cps or less, or 105 cps or less, or 100 cps or less, or 85 cps or less, or 65 cps or less, or 60 cps or less, or 55 cps or less, or 50 cps or less, or 45 cps or less, or 40 cps or less, or 35 cps or less, or 30 cps or less, and also 8 cps or more, or 10 cps or more, or 12 cps or more, or 15 cps or more, or 18 cps or more, or 20 cps or more.

[0157]

[0158] In the present invention, the viscosity of the resin and the viscosity of the monomer can be measured using a Brookfield viscometer (Brookfield DV-Ⅲ). The specific measurement method for such viscosity is as shown in Test Example 1 described below.

[0159]

[0160] In particular, the dicyclopentadiene-based epoxy resin according to the present invention is characterized in that it includes a repeating unit of the following chemical formula 1, obtained by directly thermally polymerizing an epoxy monomer and a dicyclopentadiene-based monomer in an environmentally friendly manner without using a phenol-based compound as described above.

[0161] [Chemical Formula 1]

[0162]

[0163] In the above chemical formula 1,

[0164] a and b are each independently an integer from 1 to 10,

[0165] m and n are each independently integers from 1 to 10.

[0166]

[0167] The dicyclopentadiene-based epoxy resin of the above chemical formula 1 has the NMR analysis characteristics and physical properties described above, and thus a detailed description thereof is omitted.

[0168]

[0169] Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention solely to these examples.

[0170]

[0171] <Example>

[0172] Example 1

[0173] A monomer mixture was prepared by mixing 1750 g of dicyclopentadiene (DCPD, manufacturer: YNCC, product name: DCPD, purity 80%) and 350 g of glycidyl methacrylate (GMA, manufacturer: JUNSEI, product name: glycidyl methacrylate) in 1750 g of xylene solvent. At this time, the net weight of dicyclopentadiene corresponds to 1575 g. Here, the monomer mixture is 80 wt% of dicyclopentadiene and 20 wt% of GMA.

[0174]

[0175] The above monomer composition was continuously supplied to a continuous stirred-tank reactor (CSTR; internal volume: 0.416 L), and a first thermal polymerization reaction (reaction time: 42 minutes) was performed under conditions of a temperature of 265°C and a pressure of 26 bar.

[0176]

[0177] The reaction product from the first thermal polymerization process was continuously supplied to a continuous flow reactor (PFR; Plug flow reactor, internal volume: 0.590 L) connected to the CSTR, and a second thermal polymerization reaction (reaction time: 64 minutes) was performed under conditions of a temperature of 265°C and a pressure of 26 bar.

[0178]

[0179] The product from which the above secondary thermal polymerization process was completed was dried under reduced pressure at 260°C for 30 minutes to remove the solvent, and the final polymerized dicyclopentadiene-based epoxy resin was recovered (yield 35%).

[0180]

[0181] Examples 2 to 4

[0182] In Example 1, a dicyclopentadiene-based epoxy resin was manufactured by performing the first thermal polymerization and second thermal polymerization processes in the same manner as in Example 1, except that the input amounts of DCPD and GMA were used differently as shown in Table 1 below.

[0183]

[0184] 1st Thermal Polymerization (CSTR) Reaction 2nd Thermal Polymerization (PFR) Reaction GMA (wt%) DCPD (wt%) Reaction Temperature (℃) Reaction Pressure (bar) Reaction Time (min) Reaction Temperature (℃) Reaction Pressure (bar) Reaction Time (min) Example 1 20 80 265 264 2265 2664 Example 2 30 70 265 264 2265 2664 Example 3 45 55 265 264 2265 2664 Example 4 60 40 265 264 2265 2664

[0185]

[0186] As shown in Table 1 above, in Examples 1 to 5 of the present invention, by performing a first thermal polymerization reaction on a monomer mixture containing a specific epoxy monomer and a dicyclopentadiene monomer and then performing a second thermal polymerization reaction, it can be seen that a dicyclopentadiene-based epoxy resin having a high epoxy content can be effectively manufactured in an environmentally friendly manner without using a phenol-based compound.

[0187]

[0188] Comparative Example 1

[0189] As a dicyclopentadiene (DCPD)-based fully hydrogenated resin, HC-100 (Hanwha Solutions petroleum resin commercial product) was prepared as comparative example 1.

[0190]

[0191] Comparative Example 2

[0192] YD-128 (commercial product of Kukdo Chemical) was prepared as comparative example 2 as a bisphenol A type epoxy resin.

[0193]

[0194] Comparative Example 3

[0195] YDPN-638 (commercial product of Kukdo Chemical) was prepared as comparative example 3 as a phenol novolac resin.

[0196]

[0197] <Example 1>

[0198] The following physical property evaluation was performed on the dicyclopentadiene-based epoxy resins obtained according to Examples 1 to 4, the DCPD-based fully hydrogenated resin of Comparative Example 1, the bisphenol A-type epoxy resin of Comparative Example 2, and the phenol novolac-type resin of Comparative Example 3, and the measured values ​​are shown in Table 2 below.

[0199]

[0200] a) Molecular weight measurement

[0201] Polystyrene-converted weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined by gel permeation chromatography (GPC) (Infinity1260). In addition, PDI (Mw / Mn) was calculated as the ratio of Mn to the measured Mw.

[0202]

[0203] Specifically, the dicyclopentadiene-based epoxy resins obtained according to Examples 1 to 4 and the DCPD-based completely hydrogenated resin of Comparative Example 1 were dissolved in tetrahydrofuran to a concentration of 5 wt%, and 10 μL was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, and it was introduced at a flow rate of 1 mL / min, and the analysis was performed at 35°C. The columns were connected in series with one Guard column and three PL gels 5 μm 500A, 5 μm 100A, and 5 μm 50A. A refractive index detector (RID) was used as a detector, and measurements were made at 35°C.

[0204]

[0205] b) Drying loss

[0206] 3 g of the dicyclopentadiene-based epoxy resin obtained according to Examples 1 to 4 and the DCPD-based completely hydrogenated resin of Comparative Example 1 were placed in a heat loss measuring device (AND MX-50) and heated at 200 °C for 1 hour. The weight change before and after heating was converted to a percentage to calculate the loss on drying.

[0207]

[0208] c) 1H-NMR analysis

[0209] Regarding the dicyclopentadiene-based epoxy resin obtained according to Examples 1 to 4 and the DCPD-based fully hydrogenated resin of Comparative Example 1 1 H-NMR analysis was performed and a double peak area of ​​the first peak at 3.5 ppm to 4.2 ppm and the second peak at 4.3 ppm to 4.8 ppm was confirmed.

[0210]

[0211] First, for the dicyclopentadiene-based epoxy resins synthesized according to Examples 1 to 4 1 The H-NMR analysis graphs are shown in Figures 1 to 4. In particular, the bottom of Figures 1 to 4 shows the numerical values ​​corresponding to each peak area in the entire graph, and the sum of these peak area values ​​corresponds to the entire graph area. In addition, for the dicyclopentadiene-based fully hydrogenated resin of Comparative Example 1 (HC-100, Hanwha Solutions petroleum resin commercial product) 1 The H-NMR analysis graph is shown in Figure 5.

[0212]

[0213] Specifically, the dicyclopentadiene-based epoxy resin obtained according to Examples 1 to 4 and the DCPD-based fully hydrogenated resin of Comparative Example 1 were each dissolved in the solvent CDCl3 at a concentration of 2.5 wt%, 1 H-NMR analysis (600 MHz) was performed, and the areas of the double peaks appearing in the 3.5 ppm to 4.2 ppm region (first peak) and the 4.3 ppm to 4.8 ppm region (second peak) compared to tetramethylsilane (TMS), the internal standard (TMS: 0 ppm) were confirmed. When the total sum of the entire graph peak areas obtained in this way is set as 100%, the area ratio % of the double peaks is shown in Table 2 below.

[0214]

[0215] d) Epoxy equivalent weight (EEW)

[0216] The epoxy equivalent weight (EEW) was measured for the dicyclopentadiene-based epoxy resins obtained according to Examples 1 to 4, the DCPD-based fully hydrogenated resin of Comparative Example 1, the bisphenol A-type epoxy resin of Comparative Example 2, and the phenol novolac-type resin of Comparative Example 3 according to the JIS K 7236 standard, and the unit was expressed as "g / Eq."

[0217]

[0218] Specifically, an automatic potentiometric titration device (COM-1600ST, manufactured by Hiranuma Sangyo Co., Ltd.) was used, chloroform was used as a solvent, tetraethylammonium bromide acetic acid solution was added, and titration was performed with a 0.1 mol / L perchloric acid-acetic acid solution.

[0219]

[0220] e) Glass transition temperature (Tg)

[0221] The glass transition temperature (Tg, ℃) of the dicyclopentadiene-based epoxy resins obtained according to Examples 1 to 4, the DCPD-based fully hydrogenated resin of Comparative Example 1, the bisphenol A-type epoxy resin of Comparative Example 2, and the phenol novolac-type resin of Comparative Example 3 was measured through differential scanning calorimetry (DSC) analysis.

[0222]

[0223] In particular, the glass transition temperature of the dicyclopentadiene-based epoxy resins obtained according to Examples 1 to 4, the bisphenol A-type epoxy resin of Comparative Example 2, and the phenol novolac-type resin of Comparative Example 3 was measured after curing under the following conditions, and the DCPD-based fully hydrogenated resin of Comparative Example 1 is a solid with a softening point of 100°C, so the glass transition temperature of the resin itself was measured without a separate curing process.

[0224]

[0225] Specifically, the temperature was increased from 25 ℃ to 200 ℃ at 10 ℃ / min, maintained at this temperature for 1 min, and then decreased from 200 ℃ to 25 ℃ at 10 ℃ / min and maintained for 1 min using a Differential Scanning Calorimeter (DSC, TA2000) from TA Instruments (New Castle, Delaware, USA). The temperature was then increased from 25 ℃ to 200 ℃ at 10 ℃ / min and maintained for 1 min. The melting temperature and melting point (Tm, ℃) were measured while the temperature was increased again from 25 ℃ to 200 ℃ at 10 ℃ / min (2nd cycle).

[0226]

[0227] <Conditions for measuring glass transition temperature>

[0228] - DSC device: Differential Scanning Calorimeter (DSC, device name: TA2000)

[0229] - heating rate: 10 ℃ / min

[0230] - Cooling rate: 100 ℃ / min

[0231] - temperature program: 1st and 2nd run

[0232] - temperature range: 25-200 ℃

[0233] - 2ndrun is used to measure the Tg of materials

[0234]

[0235] <Curing conditions of resins of Example 1-3 and Comparative Example 2-3>

[0236] - Type of hardener: Polyetheramine (curing agent) Huntsman D-230

[0237] - Hardener dosage (phr) = (AHEW / EEW)*100

[0238] AHEW (Active Hydrogen Equivalent Weight of Amine): Molecular Weight of Amine / Number of Active Hydrogens of Amine (D-230, 60g / eq)

[0239] EEW (Epoxy Equivalent Weight): Weight of epoxy resin containing 1 equivalent of epoxy group

[0240] Add the amount of hardener corresponding to the equivalent ratio based on 100g of DCPD epoxy resin.

[0241] - Curing conditions: 1 hour at 80 degrees in a vacuum oven, then 2 hours of curing after heating to 120 degrees (total 3 hours)

[0242] The hardener and the main agent (DCPD epoxy) were mixed using a Planetary Centrifugal Mixer at 2000 rpm for 5 minutes.

[0243]

[0244] Differential scanning calorimetry (DSC) analysis graphs measured after curing for the dicyclopentadiene-based epoxy resins synthesized according to Examples 1 to 4 as measured as described above are shown in FIGS. 6 to 9, respectively. In addition, differential scanning calorimetry (DSC) analysis graphs measured after curing for the bisphenol A-type epoxy resin of Comparative Example 2 and the phenol novolac resin of Comparative Example 3 are shown in FIGS. 10 to 11, respectively.

[0245]

[0246] Meanwhile, the specific input amounts of the main resin and the hardener during curing of the dicyclopentadiene-based epoxy resin obtained according to Examples 1 to 4, the bisphenol A-type epoxy resin of Comparative Example 2, and the phenol novolac-type resin of Comparative Example 3 are as shown in Table 2 below.

[0247]

[0248] The results of measuring the glass transition temperature after curing for the dicyclopentadiene-based epoxy resins obtained according to Examples 1 to 4, the bisphenol A-type epoxy resin of Comparative Example 2, and the phenol novolac-type resin of Comparative Example 3, and the glass transition temperature for the DCPD-based fully hydrogenated resin itself of Comparative Example 1 are shown in Table 2 below.

[0249]

[0250] f) Whether or not hydrophobic polymer fraction is included

[0251] Regarding the dicyclopentadiene-based epoxy resins obtained according to Examples 1 to 4 and the DCPD-based completely hydrogenated resin of Comparative Example 1, the bisphenol A-type epoxy resin of Comparative Example 2, and the phenol novolac-type resin of Comparative Example 3, depending on whether the molecular structure of the resin includes a “hydrophobic polymer fraction having a structure in which two or more aliphatic or aromatic rings having 5 to 60 carbon atoms are directly bonded to each other, bonded to each other via methylene, or condensed with each other”, if the above-described hydrophobic polymer fraction is included in the molecular structure of the resin, it is indicated as “O”, and if the above-described hydrophobic polymer fraction is not included in the molecular structure of the resin, it is indicated as “X”, as shown in Table 2 below.

[0252]

[0253] g) viscosity

[0254] The viscosity (cps) of the dicyclopentadiene-based epoxy resins obtained according to Examples 1 to 4, the DCPD-based fully hydrogenated resin of Comparative Example 1, the bisphenol A-type epoxy resin of Comparative Example 2, and the phenol novolac-type resin of Comparative Example 3 was measured under temperature conditions of 40°C, 60°C, 90°C, and 190°C, respectively, using a Brookfield viscometer (Brookfield DV-Ⅲ) according to ASTM D 3236.

[0255]

[0256] The viscosity measurement results of the dicyclopentadiene-based epoxy resins obtained according to Examples 1 to 4, as measured as described above, are shown in Table 2 below. The DCPD-based fully hydrogenated resin of Comparative Example 1 is a solid with a softening point of 100°C, and thus no viscosity measurement results were obtained for it.

[0257]

[0258] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 (YD-128) Comparative Example 3 (YDPN-638) Loss on drying (weight %) 30.3 30.9 32.9 34.9 28.4 Not measured Not measured Mw (g / mol) 655 70 77 75 79 9 478 Not measured Not measured Mn (g / mol) 38 24 11 46 35 14 346 Not measured Not measured PDI (Mw / Mn) 1.7 1 1.7 2 1.6 7 1.5 5 1.38 Not measured Not measured Area ratio of double peaks during NMR analysis (%) 19.5 3 2 9.7 6 4 1.8 0 5 5.3 9 0 Not measured Not measured EEW (g / Eq) 67 0 4 6 0 3 10 2 4 5 0 18 7 17 5 Tg (℃) 56.46 8.77 9.69 4.65 4.43 69.18 9Tg measurement related to curing Subject resin input (g) 100 100 100 100 Tg measurement without curing 100 100 Hardener input (g) 8.96 13.04 18.46 24 Tg measurement without curing 32.8 34.28 Inclusion of hydrophobic polymer fraction OOOOOXO Viscosity (cps) 40 ℃ Not measurable 49 300 6500 3630 Not measurable Liquid Not measurable 60 ℃ 15 400 44 30 118 0 60 2 Not measurable Liquid Not measurable 90 ℃ 6 19 310 150 97 Not measurable Liquid 761.3 190 ℃ 10 56 44 32 9.5 Not measurable Liquid 127.4

[0259]

[0260] As shown in Table 2 above, the dicyclopentadiene-based epoxy resins manufactured in an environmentally friendly manner without using a phenol-based compound according to Examples 1 to 4 of the present invention have epoxy content and glass transition temperature optimized simultaneously, and include a hydrophobic fraction within the resin molecule, and thus exhibit high heat resistance and low viscosity characteristics along with excellent hydrophobicity compared to the resins of Comparative Examples 1 to 3, and can be seen to be very advantageous in being effectively used in various fields such as IC substrates, PCBs, and flexible display substrates.

Claims

1. A step of first thermal polymerization of a monomer mixture including an epoxy monomer and a dicyclopentadiene monomer; and A step of subjecting the product obtained through the first thermal polymerization reaction to a second thermal polymerization reaction; Including, The monomer mixture comprises 10 to 60 wt% of the epoxy monomer and 90 to 40 wt% of the dicyclopentadiene monomer within 100 wt% of the total mixture. Method for producing dicyclopentadiene-based epoxy resin.

2. In paragraph 1, The above epoxy monomer is a compound containing an allyl group together with an epoxy group and having 1 to 18 carbon atoms. Method for producing dicyclopentadiene-based epoxy resin.

3. In paragraph 1, The above epoxy monomer is at least one selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, ethyl glycidyl acrylate, ethyl glycidyl methacrylate, propyl glycidyl acrylate, propyl glycidyl methacrylate, butyl glycidyl acrylate, butyl glycidyl methacrylate, 3,4-epoxy-butyl methacrylate, 6,7-epoxy-heptyl methacrylate, 3,4-epoxy-cyclohexyl methyl methacrylate, 3,4-epoxy-cyclohexyl-methyl methacrylate, 4-vinyl cyclohexene oxide, o-vinyl benzene glycidyl ether, m-vinyl benzene glycidyl ether, and p-vinyl benzene glycidyl ether. Method for producing dicyclopentadiene-based epoxy resin.

4. In paragraph 1, The above dicyclopentadiene monomer is dicyclopentadiene, Method for producing dicyclopentadiene-based epoxy resin.

5. In paragraph 1, The above monomer mixture contains 30% or more and 60% or less of the dicyclopentadiene monomer based on the weight of the epoxy monomer. Method for producing dicyclopentadiene-based epoxy resin.

6. In paragraph 1, The above first thermal polymerization reaction is performed under conditions of 255°C to 285°C. Method for producing dicyclopentadiene-based epoxy resin.

7. In paragraph 1, The above first thermal polymerization reaction is performed using a continuous stirred-tank reactor (CSTR). Method for producing dicyclopentadiene-based epoxy resin.

8. In paragraph 1, The above secondary thermal polymerization reaction is performed under conditions of 255°C to 285°C. Method for producing dicyclopentadiene-based epoxy resin.

9. In paragraph 1, The above secondary thermal polymerization reaction is performed using a continuous flow reactor (PFR; Plug flow reactor). Method for producing dicyclopentadiene-based epoxy resin.

10. A dicyclopentadiene-based epoxy resin manufactured by the method according to paragraph 1.

11. In paragraph 10, The above dicyclopentadiene-based epoxy resin is 1 When analyzed by H-NMR, it has a double peak with a first peak at 3.5 ppm to 4.2 ppm and a second peak at 4.3 ppm to 4.8 ppm. Dicyclopentadiene-based epoxy resin.

12. In paragraph 11, The area ratio of the above double peaks is 1 8% to 60% of the total graph area during H-NMR analysis, Dicyclopentadiene-based epoxy resin.

13. In paragraph 10, The above dicyclopentadiene-based epoxy resin has a weight average molecular weight (Mw) of 500 g / mol to 1000 g / mol as measured by GPC analysis. Dicyclopentadiene-based epoxy resin.

14. In paragraph 10, The above dicyclopentadiene-based epoxy resin has a number average molecular weight (Mn) of 200 g / mol to 700 g / mol as measured by GPC analysis. Dicyclopentadiene-based epoxy resin.

15. In paragraph 10, The above dicyclopentadiene-based epoxy resin has a molecular weight distribution (PDI, Mw / Mn) of 1 to 2. Dicyclopentadiene-based epoxy resin.

16. In paragraph 10, The above dicyclopentadiene-based epoxy resin has an epoxy equivalent of 200 g / eq to 1500 g / eq. Dicyclopentadiene-based epoxy resin.

17. In paragraph 10, The above dicyclopentadiene-based epoxy resin has a viscosity of 120,000 cps or less measured at 60°C according to ASTM D 3236. Dicyclopentadiene-based epoxy resin.

18. Dicyclopentadiene-based epoxy resin containing a repeating unit of the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, a and b are each independently an integer from 1 to 10, m and n are each independently integers from 1 to 10.

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