Hydrogenated dicyclopentadiene-based resin, method for preparing same, and tackifier or adhesive composition comprising same

Abstract

The present disclosure relates to a hydrogenated dicyclopentadiene-based resin comprising a bio-based material, the resin being environmentally friendly while having excellent properties including heat resistance, tackifying / adhesion properties, and the like, a method for preparing the same, and a tackifier or adhesive composition comprising the same.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Korean Patent Application No. 10-2022-0057792 filed in the Korean Intellectual Property Office on May 11, 2022, and Korean Patent Application No. 10-2023-0027510 filed in the Korean Intellectual Property Office on March 2, 2023, the disclosures of which are incorporated herein by reference in their entirety.

[0003] The present disclosure relates to a hydrogenated dicyclopentadiene-based resin that is environmentally friendly and has excellent tackifying / adhesive properties, a preparation method thereof, and a tackifier or adhesive composition including the same. [Background technology]

[0004] Dicyclopentadiene (DCPD)-based resin is a petroleum resin, which is a resin obtained by polymerizing a monomer component including dicyclopentadiene, and a hydrogenated dicyclopentadiene-based resin is mixed with various polymers such as amorphous polyalphaolefin (APAO), ethylene vinyl acetate (EVA), styrene block copolymer (SBC), etc., and used as a tackifier or a tackifier resin for an adhesive. Among them, various properties are required depending on the type and use of the tackifier or adhesive, and research and development has been actively carried out to meet these requirements.

[0005] At the same time, in order to solve the problems of carbon dioxide emissions, oil resource depletion, and plastic waste disposal, people have begun to develop biomass-based polymer materials to replace materials from oil resources. Under this trend of environmentally friendly resin development, it is necessary to develop biomass-based petroleum resins with excellent properties to replace the petroleum resins previously used as tackifiers or adhesives. [Summary of the invention]

[0006]

Technical issues

[0007] The present invention aims to provide a hydrogenated dicyclopentadiene-based resin comprising a bio-based material, a preparation method thereof, and a tackifier or adhesive composition comprising the resin, which is environmentally friendly and at the same time has excellent properties including heat resistance, tackifying / adhesive properties, etc.

[0008]

Technical solution

[0009] In order to achieve the above object, according to one embodiment of the present invention, there is provided a hydrogenated dicyclopentadiene-based resin obtained by polymerizing and hydrogenating a monomer mixture including dicyclopentadiene and vegetable oil.

[0010] The vegetable oil can be represented by the following chemical formula 1:

[0011] [Chemical formula 1]

[0012]

[0013] In Chemical Formula 1,

[0014] R1 to R3 are each independently a C5-20 alkyl group, and at least one of R1 to R3 contains one or more carbon-carbon double bonds.

[0015] The content of the vegetable oil in the monomer mixture may be 5 wt % to 20 wt %.

[0016] The monomer mixture may include dicyclopentadiene and vegetable oil in a weight ratio of 19:1 to 3:1.

[0017] The vegetable oil may have an unsaturated fatty acid content of 60 wt % to 90 wt % of the fatty acids.

[0018] The hydrogenated dicyclopentadiene-based resin according to one embodiment may have an oxygen content of about 0.1 wt % to about 5 wt %.

[0019] The hydrogenated dicyclopentadiene-based resin may have a softening point of 70°C to 120°C.

[0020] The hydrogenated dicyclopentadiene-based may have a heat loss of 3.5% or less.

[0021] The hydrogenated dicyclopentadiene-based resin may have a diacetone alcohol cloud point of 105°C or less, and a mixed methylcyclohexane-aniline cloud point of 75°C or less.

[0022] According to another embodiment of the present invention, there is provided a method for preparing a hydrogenated dicyclopentadiene-based resin, comprising the steps of: thermally polymerizing a monomer mixture comprising dicyclopentadiene and vegetable oil to prepare a polymerized dicyclopentadiene-based resin; and hydrogenating the polymerized dicyclopentadiene-based resin.

[0023] In the preparation method, the content of dicyclopentadiene in the monomer mixture may be 80 to 95 wt %, and the content of the vegetable oil may be 5 to 20 wt %.

[0024] The steps of preparing a polymerized dicyclopentadiene-based resin may include: a first polymerization stage in which a monomer mixture is thermally polymerized in a continuous stirred tank reactor (CSTR); and a second polymerization stage in which a reaction product of the first stage polymerization is thermally polymerized in a plug flow reactor (PFR).

[0025] Furthermore, according to another embodiment of the present invention, there is provided a tackifier or an adhesive composition including the hydrogenated dicyclopentadiene-based resin.

[0026]

Beneficial Effects

[0027] Since the hydrogenated dicyclopentadiene-based resin of the present invention includes a bio-based material and is thus environmentally friendly and simultaneously has excellent heat resistance, tackifying / adhesive properties, it can be usefully used as a tackifier or a tackifying resin of an adhesive composition.

Brief Description of the Drawings

[0028] Figure 1 The SAFT (Shear Adhesion Failure Temperature) measurement results of the EVA hot melt adhesives prepared using each of the resins of Examples 1 to 4 and Comparative Examples 1 to 12 are shown.

[0029] Figure 2 SAFT measurement results of mPO hot melt adhesives prepared using each of the resins of Examples 1 to 4 and Comparative Examples 1 to 12 are shown. [Specific implementation method]

[0030] The term “dicyclopentadiene-based resin” or “polymerized dicyclopentadiene-based resin” used herein refers to a polymerized resin containing dicyclopentadiene as a monomer, and “hydrogenated dicyclopentadiene-based resin” refers to a resin obtained by hydrogenating (i.e., hydrogen addition) a dicyclopentadiene-based resin.

[0031] Furthermore, the term "hydrogenation" or "hydrogen addition" refers to a reaction in which hydrogen is added to an unsaturated bond (eg, a double bond) to convert it into a single bond.

[0032] Furthermore, the term "monomer mixture" refers to a cluster of monomers in which no solvent or additive is included.

[0033] Furthermore, the term "tackifier or adhesive" is intended to include both tackifiers and adhesives.

[0034] Throughout the specification, the terms “first”, “second”, etc. are used to explain various constituent elements, and they are used merely to distinguish one constituent element from other constituent elements.

[0035] In addition, the terms used herein are only used to explain specific embodiments and are not intended to limit the present invention. Unless the context clearly indicates otherwise, singular expressions include their plural expressions. Throughout the specification, the terms "including", "equipped with" or "having" are intended to indicate the presence of implemented features, numbers, steps, constituent elements or combinations thereof, and are not intended to exclude the possibility of the presence or addition of one or more other features, numbers, steps, constituent elements or combinations thereof.

[0036] Although the present invention can be variously modified and the present invention can have various forms, specific embodiments will be illustrated and explained in detail below. However, it should be understood that this is not intended to limit the present invention to specific disclosures, and the present invention includes all modifications, equivalents or substitutes that do not depart from the spirit and technical scope of the present invention.

[0037] The hydrogenated dicyclopentadiene-based resin, the preparation method thereof, and the tackifier or adhesive composition including the same according to the present invention are described in detail below.

[0038] The hydrogenated dicyclopentadiene-based resin according to one embodiment of the present invention is obtained by polymerizing a monomer mixture containing dicyclopentadiene and vegetable oil and hydrogenating it. Therefore, the hydrogenated dicyclopentadiene-based resin contains a portion derived from dicyclopentadiene and a portion derived from vegetable oil. Although dicyclopentadiene and vegetable oil contain unsaturated bonds, when these monomers are polymerized and hydrogenated, at least a portion of the unsaturated bonds contained in the monomers can be converted into saturated bonds. Therefore, the portion derived from dicyclopentadiene and the portion derived from vegetable oil contained in the hydrogenated dicyclopentadiene-based resin may contain unsaturated bonds, respectively, or may not contain unsaturated bonds.

[0039] The inventors of the present disclosure have followed the trend of environmental protection and development of environmentally friendly resins in recent years and attempted to develop a hydrogenated dicyclopentadiene-based resin containing bio-based materials. As a result, plant oil was used as a comonomer to polymerize dicyclopentadiene, and it was confirmed that the hydrogenated dicyclopentadiene-based resin prepared by hydrogenating the obtained polymer had properties comparable to or better than those of existing dicyclopentadiene-based resins, thereby completing the present invention.

[0040] The hydrogenated dicyclopentadiene-based resin according to one embodiment of the present invention exhibits excellent heat resistance compared to existing dicyclopentadiene-based resins, and thus, it may be used as a tackifier requiring high heat resistance or an environmentally friendly tackifier resin in an adhesive composition.

[0041] Dicyclopentadiene is used as the main monomer, and a commercially available product having a purity of 75% or more, or 80% or more can be used.

[0042] The vegetable oil is a triglyceride containing unsaturated fatty acids derived from plants. Specifically, the vegetable oil can be represented by the following Chemical Formula 1:

[0043] [Chemical formula 1]

[0044]

[0045] In Chemical Formula 1,

[0046] R1 to R3 are each independently a C5-20 alkyl group, and at least one of R1 to R3 contains one or more carbon-carbon double bonds.

[0047] The type of vegetable oil is not particularly limited, for example, a vegetable oil having an unsaturated fatty acid content of 60 wt % or more, 70 wt % or more, or 90 wt % or more in fatty acids can be used. In addition, two or more vegetable oils can be used in combination as comonomers.

[0048] Specifically, the vegetable oil can be one or more selected from soybean oil, safflower oil, sunflower oil, walnut oil, corn oil, sesame oil, and peanut oil, but is not limited thereto, and various well-known vegetable oils can be used as comonomers for preparing the hydrogenated dicyclopentadiene-based resin according to one embodiment of the present invention.

[0049] At the same time, based on 100wt% of the monomer mixture, the content of the vegetable oil can be 5wt% or more, or 10wt% or more, and 20wt% or less, or 15wt% or less. Therefore, in the hydrogenated dicyclopentadiene-based resin, the portion derived from the vegetable oil can be 5wt% or more, or 10wt% or more, and 20wt% or less, or 15wt% or less. If the content of the portion derived from the vegetable oil in the hydrogenated dicyclopentadiene-based resin is less than 5wt%, it may be difficult to regard the prepared hydrogenated dicyclopentadiene-based resin as a bio-based resin, and if it is higher than 20wt%, the softening point of the prepared hydrogenated dicyclopentadiene-based resin may be reduced, and therefore, although it may be suitable as a liquid petroleum resin, it may not be suitable as a general-purpose petroleum.

[0050] According to one embodiment, the monomer mixture may include dicyclopentadiene and vegetable oil in a weight ratio of 19: 1 to 3: 1. Thus, the weight ratio of the portion derived from dicyclopentadiene to the portion derived from the vegetable oil may be 19: 1 to 3: 1.

[0051] If the proportion of dicyclopentadiene is too high, the proportion of the portion derived from vegetable oil in the hydrogenated dicyclopentadiene-based resin may be reduced, and therefore, it may not be used as a bio-based resin. On the contrary, if the proportion of vegetable oil is too high compared to dicyclopentadiene, the softening point of the hydrogenated dicyclopentadiene-based resin may be reduced, and therefore, although it can be used as a liquid petroleum resin, it may be difficult to use as a general-purpose petroleum resin. In this regard, in order to prepare a hydrogenated dicyclopentadiene-based resin suitable for use as a general-purpose petroleum resin, the weight ratio of dicyclopentadiene and vegetable oil can be 17: 1 to 3: 1, or 16: 1 to 3: 1, and therefore, the weight ratio of the portion derived from dicyclopentadiene and the portion derived from vegetable oil can be 17: 1 to 3: 1, or 16: 1 to 3: 1.

[0052] According to one embodiment of the present invention, the monomer mixture for preparing the hydrogenated dicyclopentadiene-based resin may not contain other monomers except dicyclopentadiene and vegetable oil. That is, the hydrogenated dicyclopentadiene-based resin may only contain a portion derived from dicyclopentadiene and a portion derived from vegetable oil.

[0053] Alternatively, the monomer mixture may further comprise a comonomer in addition to dicyclopentadiene and the vegetable oil. Preferably, the content of the additional comonomer may be 30 wt % or less, or 20 wt % or less, based on 100 wt % of the mixture. Thus, the hydrogenated dicyclopentadiene-based resin may comprise a portion derived from the additional comonomer in an amount of 30 wt % or less, or 20 wt % or less.

[0054] As the additional comonomer, a comonomer conventionally used for preparing a dicyclopentadiene-based resin may be used without limitation, and for example, piperylene (PIP), styrene, or a combination thereof may be used.

[0055] The weight average molecular weight (Mw) of the hydrogenated dicyclopentadiene-based resin is not particularly limited, and may be, for example, 400 g / mol or more, 500 g / mol or more, 600 g / mol or more, or 650 g / mol or more, and 2000 g / mol or less, 1800 g / mol or less, 1600 g / mol or less, or 1500 g / mol or less.

[0056] Furthermore, the polydispersity index (PDI) of the hydrogenated dicyclopentadiene-based resin may be, for example, 1.0 or more, or 1.3 or more, or 1.5 or more, and 3.0 or less, or 2.7 or less, or 2.5 or less.

[0057] The weight average molecular weight (Mw) and polydispersity index of the hydrogenated dicyclopentadiene-based resin may be measured using gel permeation chromatography (GPC), as shown in the following Experimental Examples.

[0058] Since the hydrogenated dicyclopentadiene-based resin is prepared using vegetable oil as a comonomer, its oxygen content can meet 0.1wt% or more. Specifically, the oxygen content of the hydrogenated dicyclopentadiene-based resin can be 0.1wt% or more, 0.3wt% or more, or 0.4wt% or more, and 5wt% or less, 3wt% or less, or 2.7wt% or less.

[0059] Therefore, since the hydrogenated dicyclopentadiene-based resin according to one embodiment of the present invention exhibits a higher oxygen content than the existing dicyclopentadiene-based resin, it may exhibit more excellent solubility to a polar solvent and have improved compatibility with a polar substrate.

[0060] The hydrogenated dicyclopentadiene-based resin may have a softening point of 70° C. or more, 80° C. or more, or 90° C. or more, and 120° C. or less, 110° C. or less, or 105° C. or less. When the hydrogenated dicyclopentadiene-based resin satisfies the above softening point range, it may be suitably used as a general-purpose hot melt adhesive.

[0061] In addition, the hydrogenated dicyclopentadiene-based resin exhibits an excellent heat loss of 3.5% or less, preferably 3.2% or less, or 3.0% or less. The lower the heat loss, the better, and theoretically it can be 0%.

[0062] The hydrogenated dicyclopentadiene-based resin exhibits excellent solubility to a solvent.

[0063] Specifically, the hydrogenated dicyclopentadiene-based resin may satisfy a diacetone alcohol cloud point (DACP) of 105° C. or less, 104° C. or less, or 102° C. or less, and 60° C. or more, 70° C. or more, or 80° C. or more.

[0064] Further, the hydrogenated dicyclopentadiene-based resin may satisfy a mixed methylcyclohexane-aniline cloud point (MMAP) of 75° C. or less, or 72° C. or less, or 71° C. or less, and 50° C. or more, or 60° C. or more.

[0065] The measurement methods of oxygen content, softening point, heat loss, diacetone alcohol cloud point and mixed methylcyclohexane-aniline cloud point will be specifically described in the following experimental examples.

[0066] The hydrogenated dicyclopentadiene-based resin may be prepared by a preparation method comprising the steps of: thermally polymerizing a monomer mixture including dicyclopentadiene and a vegetable oil to prepare a polymerized dicyclopentadiene-based resin; and hydrogenating the polymerized dicyclopentadiene-based resin.

[0067] The vegetable oil included in the monomer mixture is as described above.

[0068] The monomer mixture may not further include other monomers except dicyclopentadiene and vegetable oil. At this time, the content of dicyclopentadiene in the monomer mixture may be 80wt% to 95wt%, and the content of vegetable oil may be 5wt% to 20wt%. Alternatively, based on 100wt% of the monomer mixture, the content of dicyclopentadiene may be 80wt% to 95wt%, and the content of vegetable oil may be 10wt% to 15wt%.

[0069] Alternatively, the monomer mixture may further comprise an additional comonomer in addition to dicyclopentadiene and vegetable oil, wherein the additional comonomer and the amount used are as described above.

[0070] The monomer mixture can be added to the thermal polymerization while being dissolved in a solvent, i.e. in the form of a monomer composition. There is no particular limitation on the solvent that can be used when preparing the monomer composition, for example, one or more selected from pentane, hexane, heptane, nonane, decane, benzene, toluene, and xylene can be used.

[0071] Furthermore, the monomer composition may further include additives commonly used in the technical field to which the present invention belongs, such as antioxidants, polymerization inhibitors, and the like.

[0072] The method for thermally polymerizing the monomer mixture containing dicyclopentadiene and vegetable oil is not particularly limited, and for example, can be prepared by a method comprising: a) a first polymerization stage, in which the monomer mixture is thermally polymerized in a continuous stirred tank reactor (CSTR); and b) a second polymerization stage, in which the reaction product of the first stage polymerization is thermally polymerized in a plug flow reactor (PFR). The monomer mixture can be used in the form of a monomer composition dissolved in a solvent.

[0073] Thus, in the case where thermal polymerization is performed in two stages, the polymerization heat can be controlled, and the conversion rate or polymerization rate of the monomer can be significantly improved, and a dicyclopentadiene-based resin having a narrow molecular weight distribution and thus uniform properties can be provided.

[0074] The reaction temperature (T1) in step a) may be 210 to 270° C., or 220 to 270° C. If the polymerization is performed within the above reaction temperature range, the conversion rate of the monomer or the polymerization rate is excellent, and side reactions such as cross-linking may be suppressed.

[0075] The reaction pressure in step a) can be 1 to 40 bar, or 5 to 35 bar, or 10 to 30 bar. If the polymerization is carried out under the above reaction pressure, the reactivity of the monomer can be improved without causing safety accidents.

[0076] The reaction time in step a) can be set to 10 to 90 minutes, or 20 to 80 minutes, or 30 to 70 minutes. If the reaction time is too short, the inhibition of the side reaction caused by the mixing of the raw materials may be insufficient, and if the reaction time is too long, the productivity of the final resin may decrease, and the molecular weight distribution may become broad, therefore, it is preferred that the reaction time is controlled within the above range.

[0077] The reaction temperature (T2) in step b) may be within the range of ±30° C. of the reaction temperature (T1) in step a), i.e., T1-30° C. to T1+30° C., or T1-20° C. to T1+20° C., or T1-15° C. to T1+15° C. If the polymerization is carried out within the above reaction temperature range, side reactions can be suppressed and productivity can be improved.

[0078] Also, by controlling the temperature difference between step a) and step b) within ±30° C., the generation of unreacted oligomers can be minimized, and a dicyclopentadiene-based resin having a narrow molecular weight distribution can be prepared.

[0079] The reaction pressure in step b) may be 1 to 40 bar, or 5 to 35 bar, or 10 to 30 bar. If the reaction pressure is too low, the reactivity may be low due to evaporation of the monomer, and if the pressure is too high, the risk of safety accidents during the process may be high, and therefore, the reaction pressure is preferably controlled within the above range.

[0080] The reaction time in step b) can be 1 to 4 times, or 1 to 3 times, or 1 to 2 times the reaction time in step a). If the reaction time is too short compared to the reaction time in step a), the reaction may not be fully carried out, and if the reaction time is too long, side reactions may occur, therefore, it is preferred that the reaction time be controlled within the above range.

[0081] In addition, the internal volume of the PFR used in the polymerization of step b) may be set to 1 to 3 times, or 1 to 2.5 times, or 1 to 2 times the internal volume of the CSTR used in the polymerization of step a). If the internal volume of the PFR is too small relative to the internal volume of the CSTR, the polymerization in the PFR may not be sufficiently carried out, and thus a large amount of impurities such as wax may remain, and if the internal volume of the PFR is too large relative to the internal volume of the CSTR, the effect of applying the CSTR may not be significant, and thus the control of the initial reaction heat may be insufficient, and it may be difficult to control the reaction temperature, and therefore, it is preferred that the internal volume of the PFR be controlled within the above range.

[0082] The hydrogenation or hydrogen addition is not particularly limited and may be performed according to any method known in the art. Hydrogenation is a reaction in which an unsaturated bond such as a double bond is hydrogenated to convert it into a single bond, and a hydrogenated dicyclopentadiene-based resin may be obtained from a polymerized dicyclopentadiene-based resin by hydrogenation.

[0083] The hydrogenation can be performed according to methods known in the art. For example, the hydrogenation can be performed by adding the obtained polymerized dicyclopentadiene-based resin to a continuous hydrogenation reactor containing a hydrogenation catalyst.

[0084] The hydrogenation catalyst is not particularly limited, and any hydrogenation catalyst known in the art can be used. Specifically, one or more selected from Ni, Fe, Cu, Co, Mo, Pd, Rh, Pt, Nb, Au, Rd and Raney nickel can be used as the hydrogenation catalyst.

[0085] The hydrogenation catalyst may be used in an amount of 0.1 parts by weight or more, or 0.3 parts by weight or more, or 0.5 parts by weight or more, and 1.0 parts by weight or less, or 0.8 parts by weight or less, based on 100 parts by weight of the polymerized dicyclopentadiene-based resin, to improve reactivity, but the amount is not limited thereto.

[0086] The hydrogenation conditions are not particularly limited, and for example, it may be performed at 150 to 300° C. and a pressure of 50 to 150 bar. In the case where the hydrogenation is performed at the above pressure and temperature, the destruction of the molecular structure may be prevented.

[0087] Furthermore, hydrogen can be added continuously so that the reaction pressure can be kept constant during the hydrogenation.

[0088] The above hydrogenated dicyclopentadiene-based resin can be used as a hot melt adhesive or a pressure-sensitive adhesive, etc., or can be mixed with various base resins, for example, one or more base resins selected from ethylene-vinyl acetate resins, polyolefin-based resins, polyester-based resins, styrene-based resins, polyamide-based resins, and ethylene-acryl-based resins, and used as an adhesive or a tackifier. In addition, it can be used as a tackifier or adhesive resin in inks, coatings, road marking paints, etc.

[0089] The following will describe the functions and effects of the present invention in more detail through the specific embodiments of the present invention. However, these embodiments are only examples of the present invention and are not intended to determine the scope of the present invention.

[0090] [Example]

[0091] Example 1

[0092] A monomer composition was prepared by mixing 1425 g of dicyclopentadiene (purity 80%), 75 g of soybean oil and 1500 g of xylene solvent.

[0093] The monomer composition was continuously fed into a continuous stirred tank reactor (CSTR, internal volume: 0.416 L) to carry out first stage polymerization at a temperature of 265° C. and a pressure of 25 bar (reaction time: 43 minutes).

[0094] While the reaction product of the first stage polymerization was continuously fed into a plug flow reactor (PFR, internal volume: 0.590 L) connected to a CSTR, the second stage polymerization was carried out at a temperature of 278° C. and a pressure of 25 bar (reaction time: 67 minutes).

[0095] The polymerization product was decompressed at 260° C. for 30 minutes, and the polymerized dicyclopentadiene-based resin was recovered.

[0096] The polymerized dicyclopentadiene-based resin was fed into a fixed bed reactor with a length of 1.5 m, loaded with 0.5 wt% of a heterogeneous palladium catalyst, and hydrogenated at a reaction temperature of 250° C., a reaction pressure of 100 bar, a raw material flow rate of 40 ml / min, and a hydrogen flow rate of 4 NMPL based on 100 wt% of the polymerized dicyclopentadiene-based resin to prepare a hydrogenated dicyclopentadiene-based resin.

[0097] Example 2

[0098] A polymerized dicyclopentadiene-based resin and a hydrogenated dicyclopentadiene-based resin were prepared in the same manner as in Example 1, except that 1350 g of dicyclopentadiene and 150 g of soybean oil were used as monomers, and the CSTR reaction temperature was set to 270° C. and the PFR reaction temperature was set to 280° C.

[0099] Example 3

[0100] A polymerized dicyclopentadiene-based resin and a hydrogenated dicyclopentadiene-based resin were prepared in the same manner as in Example 1, except that 1275 g of dicyclopentadiene and 225 g of soybean oil were used as monomers, and the CSTR reaction temperature was set to 270° C. and the PFR reaction temperature was set to 280° C.

[0101] Example 4

[0102] A polymerized dicyclopentadiene-based resin and a hydrogenated dicyclopentadiene-based resin were prepared in the same manner as in Example 1, except that 1200 g of dicyclopentadiene and 300 g of soybean oil were used as monomers, and the CSTR reaction temperature was set to 275° C. and the PFR reaction temperature was set to 280° C.

[0103] The oxygen content (wt %) of each hydrogenated dicyclopentadiene-based resin prepared in Examples 1 to 4 was measured, and the results are shown in the following Table 1. In addition, infrared spectroscopy (IR) analysis was performed on each hydrogenated dicyclopentadiene-based resin.

[0104]

Table 1

[0105]

[0106] IR analysis of each of the hydrogenated dicyclopentadiene-based resins of Examples 1 to 4 showed that -1 A peak of carbonyl group derived from vegetable oil was confirmed at . In addition, as a result of measurement of the actual oxygen content of the hydrogenated dicyclopentadiene-based resin, it was confirmed that it was similar to the predicted oxygen content calculated from the input amount of soybean oil.

[0107] From these results, it can be confirmed that vegetable oil (soybean oil) is polymerized with DCPD as a comonomer and included in the polymer chain.

[0108] Comparative Example 1

[0109] As Comparative Example 1, HC-100 (from Hanwha solutions) was used.

[0110] Comparative Example 2

[0111] As Comparative Example 2, HC-120 (from Hanwha Solutions) was used.

[0112] Comparative Example 3

[0113] 95 parts by weight of HC-100 (from Hanwha Solutions) and 5 parts by weight of soybean oil were mixed and used as Comparative Example 3.

[0114] Comparative Example 4

[0115] 85 parts by weight of HC-100 (from Hanwha Solutions) and 15 parts by weight of soybean oil were mixed and used as Comparative Example 4.

[0116] Comparative Example 5

[0117] 75 parts by weight of HC-100 (from Hanwha Solutions) and 25 parts by weight of soybean oil were mixed and used as Comparative Example 5.

[0118] Comparative Example 6

[0119] 95 parts by weight of HC-120 (from Hanwha Solutions) and 5 parts by weight of soybean oil were mixed and used as Comparative Example 6.

[0120] Comparative Example 7

[0121] 85 parts by weight of HC-120 (from Hanwha Solutions) and 15 parts by weight of soybean oil were mixed and used as Comparative Example 7.

[0122] Comparative Example 8

[0123] 75 parts by weight of HC-120 (from Hanwha Solutions) and 25 parts by weight of soybean oil were mixed and used as Comparative Example 8.

[0124] Comparative Example 9

[0125] The soybean oil was fed into a fixed bed reactor with a length of 1.5 m, loaded with a heterogeneous palladium catalyst (0.5 wt%, based on 100 wt% polymerized dicyclopentadiene-based resin), and hydrogenated at a reaction temperature of 250° C., a reaction pressure of 100 bar, a raw material flow rate of 40 ml / min, and a hydrogen flow rate of 4 NMPL to prepare hydrogenated soybean oil.

[0126] 85 parts by weight of HC-100 (from Hanwha Solutions) and 15 parts by weight of the hydrogenated soybean oil were mixed and used as Comparative Example 9.

[0127] Comparative Example 10

[0128] Hydrogenated soybean oil was prepared in the same manner as in Comparative Example 9, and 75 parts by weight of HC-100 (from Hanwha Solutions) and 25 parts by weight of hydrogenated soybean oil were mixed and used as Comparative Example 10.

[0129] Comparative Example 11

[0130] Hydrogenated soybean oil was prepared in the same manner as in Comparative Example 9, and 85 parts by weight of HC-120 (from Hanwha Solutions) and 15 parts by weight of hydrogenated soybean oil were mixed and used as Comparative Example 11.

[0131] Comparative Example 12

[0132] Hydrogenated soybean oil was prepared in the same manner as in Comparative Example 9, and 75 parts by weight of HC-120 (from Hanwha Solutions) and 25 parts by weight of hydrogenated soybean oil were mixed and used as Comparative Example 11.

[0133] Experimental Examples

[0134] (1) Softening point

[0135] The softening point of each resin was measured twice using Anton Paar RKA5 equipment according to ASTM E 28, and the average value was calculated and shown in Table 1.

[0136] (2) Molecular weight

[0137] The weight average molecular weight (polystyrene conversion, Mw), number average molecular weight (Mn) and Z average molecular weight (Mz) were measured by gel permeation chromatography (GPC) (Viscotek TDA302 and Agilent 1200 series (pump)).

[0138] The resin to be tested was dissolved in tetrahydrofuran at a concentration of 4000 ppm, and 100 μl of the solution was injected into the GPC. Tetrahydrofuran was used as the mobile phase of the GPC at a flow rate of 1.0 mL / min and the analysis was performed at 35°C. Agilent PLMixed C 2set+PL As a chromatographic column. RI detector (Viscotek RI) was used as a detector for measurement at 35°C. A calibration curve formed after measuring polystyrene standards was used to obtain Mw, Mn and Mz values. Twelve types with molecular weights of 104 / 118 / 236 / 580 / 1480 / 2340 / 2970 / 5030 / 8450 / 10850 / 20650 / 24600 were used as polystyrene standards.

[0139] Here, PDI (polydispersity index) is calculated by dividing the measured weight average molecular weight by the number average molecular weight.

[0140] (3) Heat loss

[0141] 3 g of the resin was added to a thermogravimetric analyzer (AND MX-50) and heated at 180° C. for 1 hour. The weight change before and after heating was converted into a percentage to calculate the heat loss.

[0142] (4) Melt viscosity (ASTM D 3236)

[0143] The viscosity of the resin at 180°C was measured using a Brookfield DV-III viscometer.

[0144] (5) Diacetone alcohol cloud point (DACP)

[0145] A mixed solution of 5 g of resin, 5 g of xylene, and 5 g of diacetone alcohol was prepared, and the solution was heated until it became transparent, and then the temperature at which the solution became turbid was measured while the solution was cooled to obtain DACP.

[0146] (6) Mixed methylcyclohexane-aniline cloud point (MMAP)

[0147] A mixed solution of 5 g of resin, 5 g of methylcyclohexane, and 5 g of aniline was prepared, and the solution was heated until it became transparent. The temperature at which the solution became turbid was measured while the solution was cooled to obtain MMAP.

[0148] (7) Shear Adhesion Failure Temperature (SAFT)

[0149] The base resin, each resin of the comparative example and the example, and the Fischer-Tropsch wax were mixed in a mixing ratio of 4:4:2 to prepare a hot melt adhesive (HMA). Afterwards, an HMA film having a certain thickness was manufactured by a hot press (QM900A, Qmesys), and then the manufactured film was cut into 2.5*2.5 cm squares and bonded to a B-type corrugated cardboard made of KLB to manufacture a SAFT measurement sample.

[0150] While applying a load of 500 g to the manufactured SAFT sample using a SAFT measurement device (Elastocon Corporation, ES-07II), the temperature was increased by 1° C. every 2 minutes, and the temperature at which the HMA lost adhesion and the sample was separated was measured.

[0151] As base resins, EVA1529 (Hanwha Solutions) was used as the EVA hot melt adhesive, and GA1900 (DOW) was used as the mPO hot melt adhesive.

[0152] The SAFT measurement results of EVA hot melt adhesive are shown in Figure 1 and the SAFT measurement results of mPO hot melt adhesive are shown in Figure 2 Meanwhile, the resin of Comparative Example 5 was in a sticky semi-solid state when using mPO as the base resin, and thus the mPO hot melt adhesive could not be manufactured.

[0153]

Table 2

[0154]

[0155]

Table 3

[0156]

[0157]

Table 4

[0158]

[0159] Referring to Table 1, it can be confirmed that the hydrogenated dicyclopentadiene-based resins of Examples 1 to 4 have higher molecular weights than existing petroleum resins due to the presence of soybean oil, and achieve properties at the same level as commercial petroleum resins, including softening point, heat loss, DACP, MMAP, etc.

[0160] In addition, refer to Figure 1 and Figure 2It can be confirmed that the EVA hot melt adhesive and mPO hot melt adhesive produced using the resins of Examples 1 to 4 exhibit heat resistance equal to or superior to that of existing commercially available petroleum resins. However, in Comparative Examples 3 to 8 in which soybean oil was not copolymerized but simply mixed with commercially available petroleum resins, and Comparative Examples 9 to 12 in which hydrogenated soybean oil was mixed with commercially available petroleum resins, heat resistance was deteriorated.

Claims

1. A hydrogenated dicyclopentadiene-based resin obtained by polymerization and hydrogenation of a monomer mixture comprising dicyclopentadiene and a vegetable oil.

2. The hydrogenated dicyclopentadiene-based resin according to claim 1, wherein Vegetable oil is represented by the following chemical formula 1: [Chemical formula 1] In Chemical Formula 1, R1 to R3 are each independently a C5-20 alkyl group, and at least one of R1 to R3 contains one or more carbon-carbon double bonds.

3. The hydrogenated dicyclopentadiene-based resin according to claim 1 or claim 2, wherein the content of the vegetable oil in the monomer mixture is 5 wt% to 20 wt%.

4. The hydrogenated dicyclopentadiene-based resin according to any one of claims 1 to 3, wherein the monomer mixture comprises dicyclopentadiene and vegetable oil in a weight ratio of 19:1 to 3:

1.

5. The hydrogenated dicyclopentadiene-based resin according to any one of claims 1 to 4, wherein the vegetable oil has an unsaturated fatty acid content of 60 wt% to 90 wt% in fatty acids.

6. The hydrogenated dicyclopentadiene-based resin according to any one of claims 1 to 5, wherein The hydrogenated dicyclopentadiene-based resin has an oxygen content of about 0.1 wt % to about 5 wt %. 7 . The hydrogenated dicyclopentadiene-based resin according to any one of claims 1 to 6 , wherein the hydrogenated dicyclopentadiene-based resin has a softening point of 70° C. to 120° C.

8. The hydrogenated dicyclopentadiene-based resin according to any one of claims 1 to 7, wherein The hydrogenated dicyclopentadiene-based resin has a heat loss of 3.5% or less.

9. The hydrogenated dicyclopentadiene-based resin according to any one of claims 1 to 8, wherein the hydrogenated dicyclopentadiene-based resin has a diacetone alcohol cloud point of 105°C or less, and a mixed methylcyclohexane-aniline cloud point of 75°C or less.

10. A method for preparing a hydrogenated dicyclopentadiene-based resin comprising the following steps: thermally polymerizing a monomer mixture comprising dicyclopentadiene and a vegetable oil to prepare a polymerized dicyclopentadiene-based resin; as well as The polymerized dicyclopentadiene-based resin is hydrogenated.

11. The method for preparing a hydrogenated dicyclopentadiene-based resin according to claim 10, wherein: The content of dicyclopentadiene in the monomer mixture is 80 to 95 wt %, and the content of the vegetable oil is 5 to 20 wt %.

12. The method for preparing a hydrogenated dicyclopentadiene-based resin according to claim 10 or 11, wherein: The steps for preparing a polymerized dicyclopentadiene-based resin include: a first polymerization stage, in which the monomer mixture is thermally polymerized in a continuous stirred tank reactor (CSTR); and The second polymerization stage, in which the reaction product of the first stage polymerization is thermally polymerized in a plug flow reactor (PFR).

13. A tackifier or adhesive composition comprising the hydrogenated dicyclopentadiene-based resin according to any one of claims 1 to 9.

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