Hydrogenated dicyclopentadiene resin, its production method, and pressure-sensitive adhesive composition containing the same

Abstract

The present invention relates to a hydrogenated dicyclopentadiene resin that is environmentally friendly because it contains bio-based raw materials and yet has excellent physical properties such as heat resistance and adhesive properties, a production method thereof, and a pressure-sensitive adhesive composition containing the same.

Description

[Technical field]

[0001] [CROSS REFERENCE TO RELATED APPLICATIONS] This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0057792 dated May 11, 2022 and Korean Patent Application No. 10-2023-0027510 dated March 2, 2023, and all contents disclosed in the documents of said Korean patent applications are incorporated herein by reference.

[0002] The present invention relates to a hydrogenated dicyclopentadiene resin which is environmentally friendly and has excellent pressure-sensitive adhesive properties, a method for producing the same, and a pressure-sensitive adhesive composition containing the same. [Background technology]

[0003] Dicyclopentadiene (DCPD) resin, a type of petroleum resin, is a resin polymerized from monomer components including dicyclopentadiene, and hydrogenated dicyclopentadiene resin is mixed with various polymers such as amorphous polyalphaolefin (APAO), ethylenevinyl acetate (EVA), and styrenic block copolymers (SBCs) to be used as a tackifier resin for adhesives. At this time, various physical properties are required depending on the type and application of the adhesive, and in order to meet this, research and development is being actively conducted to improve compatibility with polymers and adhesive strength.

[0004] On the other hand, as a measure to solve the problems of carbon dioxide emissions, depletion of petroleum resources, and plastic waste disposal, polymer materials made from biomass instead of petroleum-derived raw materials are being developed. Due to this trend in the development of environmentally friendly resins, there is a demand for the development of bio-based petroleum resins with excellent physical properties that can replace the petroleum resins that have been used as adhesives in the past. Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a hydrogenated dicyclopentadiene resin that is environmentally friendly because it contains bio-based raw materials and yet has excellent physical properties such as heat resistance and adhesive properties, a production method thereof, and a pressure-sensitive adhesive composition containing the same. [Means for solving the problem]

[0006] In order to solve the above problems, according to one embodiment of the present invention, A hydrogenated dicyclopentadiene resin is provided which is obtained by polymerization and hydrogenation of a monomer mixture containing dicyclopentadiene and vegetable oil.

[0007] The vegetable oil may be represented by the following formula 1: [ka] In the above Chemical Formula 1, R 1 ~R 3 are each independently an alkyl group having 5 to 20 carbon atoms, 1 ~R 3 At least one of the groups contains one or more carbon-carbon double bonds.

[0008] The content of the vegetable oil in the monomer mixture may be 5% by weight to 20% by weight.

[0009] The monomer mixture may contain dicyclopentadiene and vegetable oil in a weight ratio of 19:1 to 3:1.

[0010] The vegetable oil may have fatty acids with a content of unsaturated fatty acids of 60% by weight to 90% by weight.

[0011] The hydrogenated dicyclopentadiene resin according to one embodiment may have an oxygen content of 0.1% by weight to 5% by weight.

[0012] The hydrogenated dicyclopentadiene resin may have a softening point of 70°C to 120°C.

[0013] The hydrogenated dicyclopentadiene resin may have a loss on drying of 3.5% or less.

[0014] The hydrogenated dicyclopentadiene resin may have a diacetone cloud point of 105° C. or lower and a mixed methylcyclohexane-aniline cloud point of 75° C. or lower.

[0015] According to another embodiment of the present invention, there is provided a method for producing a hydrogenated dicyclopentadiene-based resin, the method including: thermally polymerizing a monomer mixture containing dicyclopentadiene and a vegetable oil to produce a polymerized dicyclopentadiene-based resin; and hydrogenating the polymerized dicyclopentadiene-based resin.

[0016] In the above-mentioned production method, the content of dicyclopentadiene in the monomer mixture may be 80 to 95% by weight, and the content of the vegetable oil may be 5 to 20% by weight.

[0017] The step of preparing the polymerized dicyclopentadiene-based resin may include a first-stage polymerization in which a monomer mixture is thermally polymerized in a continuous stirred tank reactor (CSTR); and a second-stage polymerization in which the reaction product of the first-stage polymerization is thermally polymerized in a plug flow reactor (PFR).

[0018] According to another embodiment of the present invention, there is provided a pressure-sensitive adhesive composition comprising the hydrogenated dicyclopentadiene resin. Effect of the Invention

[0019] The hydrogenated dicyclopentadiene resin of the present invention is environmentally friendly because it contains bio-based raw materials, and yet has excellent physical properties such as solubility, heat resistance, and adhesive properties, and can be usefully used as a tackifier resin in adhesive compositions. [Brief description of the drawings]

[0020] [Figure 1]1 shows the results of SAFT (Shear Adhesion Failure Temperature) measurement for EVA hot melt adhesives produced using the resins of Examples 1 to 4 and Comparative Examples 1 to 12. [Diagram 2] 1 shows the results of SAFT measurements of mPO hot melt adhesives produced using the resins of Examples 1 to 4 and Comparative Examples 1 to 12. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] As used herein, the term "dicyclopentadiene-based resin" or "polymerized dicyclopentadiene-based resin" means a resin polymerized containing dicyclopentadiene as a monomer, and the term "hydrogenated dicyclopentadiene-based resin" means a resin obtained by subjecting the dicyclopentadiene-based resin to a hydrogenation reaction, i.e., a hydrogenation reaction.

[0022] The term "hydrogenation" or "hydrogen addition reaction" refers to a reaction in which hydrogen is added to an unsaturated bond such as a double bond to convert it into a single bond.

[0023] Additionally, the term "monomer mixture" refers to a collection of monomers that does not contain solvents or additives.

[0024] The term "adhesive" is used in a comprehensive sense to include both tackifiers and adhesives.

[0025] In the present invention, the terms first, second, etc. are used to describe various components, and the terms are used only to distinguish one component from another.

[0026] In addition, the terms used in this specification are merely used to describe exemplary embodiments and are not intended to limit the present invention. A singular expression includes a plural expression unless the context clearly indicates otherwise. In this specification, the terms "include", "comprise", "have" or "have" are intended to specify the presence of an implemented feature, step, component, or combination thereof, and should be understood not to preclude the possibility of the presence or addition of one or more other features, steps, components, or combinations thereof.

[0027] Although the present invention can be modified in various ways and has various forms, specific embodiments are exemplified and described in detail below. However, it is not intended to limit the present invention to the specific disclosed embodiments, and it should be understood that the present invention includes all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0028] The hydrogenated dicyclopentadiene resin of the present invention, its production method, and pressure-sensitive adhesive composition containing the same will be described in more detail below.

[0029] The hydrogenated dicyclopentadiene-based resin according to an embodiment of the present invention is obtained by polymerization and hydrogenation of a monomer mixture containing dicyclopentadiene and vegetable oil. Thus, the hydrogenated dicyclopentadiene-based resin includes a moiety derived from dicyclopentadiene and a moiety derived from vegetable oil. The dicyclopentadiene and vegetable oil contain unsaturated bonds, but at least a part of the unsaturated bonds contained in the monomers can be converted to saturated bonds when these monomers are polymerized and hydrogenated. Thus, the dicyclopentadiene-derived moiety and the vegetable oil-derived moiety contained in the hydrogenated dicyclopentadiene-based resin may or may not contain unsaturated bonds.

[0030] In response to the recent trend of environmental protection and development of environmentally friendly resins, the present inventors have been making efforts to develop a hydrogenated dicyclopentadiene-based resin containing a bio-based raw material. As a result, they have confirmed that a hydrogenated dicyclopentadiene-based resin produced by polymerizing dicyclopentadiene together with a vegetable oil as a comonomer and hydrogenating the resulting polymer has physical properties equal to or greater than those of existing dicyclopentadiene-based resins, thereby completing the present invention.

[0031] The hydrogenated dicyclopentadiene resin according to one embodiment of the present invention exhibits superior heat resistance compared to existing dicyclopentadiene resins, and can therefore be usefully used as an environmentally friendly tackifier resin for adhesive compositions that require high heat resistance.

[0032] The 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.

[0033] The vegetable oil is a triglyceride containing unsaturated fatty acids derived from plants. Specifically, the vegetable oil may be represented by the following chemical formula 1: [ka] In the above Chemical Formula 1, R 1 ~R 3 are each independently an alkyl group having 5 to 20 carbon atoms, 1 ~R 3 At least one of the groups contains one or more carbon-carbon double bonds.

[0034] The type of the vegetable oil is not particularly limited, but for example, a vegetable oil having an unsaturated fatty acid content of 60% by weight or more, or 70% by weight or more and 90% by weight or less in fatty acids may be used. In addition, two or more different vegetable oils may be combined and used as a comonomer.

[0035] Specifically, the vegetable oil may be at least one selected from the group consisting of soybean oil, safflower oil, sunflower oil, walnut oil, corn oil, sesame oil, and peanut oil, but is not limited thereto. Various types of widely known vegetable oils can be used as a comonomer for producing the hydrogenated dicyclopentadiene-based resin according to one embodiment of the present invention.

[0036] On the other hand, the content of the vegetable oil in 100% by weight of the monomer mixture may be 5% by weight or more, or 10% by weight or more, and 20% by weight or less, or 15% by weight or less. Thus, the portion derived from the vegetable oil in the hydrogenated cyclopentadiene resin may be 5% by weight or more, or 10% by weight or more, and 20% by weight or less, or 15% by weight or less. If the content of the portion derived from the vegetable oil in the hydrogenated cyclopentadiene resin is less than 5% by weight, the hydrogenated dicyclopentadiene resin produced is difficult to be regarded as a bio-based resin, and if it exceeds 20% by weight, the softening point of the hydrogenated dicyclopentadiene resin produced is lowered, so that it is suitable as a liquid petroleum resin but may not be suitable as a general-purpose petroleum resin.

[0037] In one embodiment, the monomer mixture may include dicyclopentadiene and vegetable oil in a weight ratio of 19:1 to 3:1, whereby the weight ratio of the portion derived from dicyclopentadiene to the portion derived from vegetable oil may be 19:1 to 3:1.

[0038] If the ratio of dicyclopentadiene is too high, the ratio of the vegetable oil-derived portion in the hydrogenated dicyclopentadiene resin is reduced, so that the hydrogenated dicyclopentadiene resin cannot function as a bio-based resin. Conversely, if the ratio of vegetable oil to dicyclopentadiene is too high, the softening point of the hydrogenated dicyclopentadiene resin may be lowered, and although it can be used as a liquid petroleum resin, it may be difficult to utilize it as a general-purpose petroleum resin. From this perspective, in order to produce a hydrogenated dicyclopentadiene resin suitable as a general-purpose petroleum resin, the weight ratio of dicyclopentadiene and vegetable oil may be 17:1 to 3:1, or 16:1 to 3:1, and thus the weight ratio of the portion derived from dicyclopentadiene to the portion derived from vegetable oil may be 17:1 to 3:1, or 16:1 to 3:1.

[0039] The monomer mixture for producing the hydrogenated dicyclopentadiene-based resin according to the embodiment of the present invention may not further include other monomers in addition to dicyclopentadiene and vegetable oil, that is, the hydrogenated dicyclopentadiene-based resin may include only a portion derived from dicyclopentadiene and a portion derived from vegetable oil.

[0040] Alternatively, the monomer mixture may further include an additional comonomer in addition to dicyclopentadiene and vegetable oil. The content of such additional comonomer is preferably 30% by weight or less, or 20% by weight or less, based on 100% by weight of the monomer mixture. Thus, the hydrogenated dicyclopentadiene-based resin may include a portion derived from the additional comonomer in an amount of 30% by weight or less, or 20% by weight or less.

[0041] As the additional comonomer, any comonomer that is conventionally used in the preparation of dicyclopentadiene-based resins may be used without limitation. For example, piperylene (PIP), styrene, or a combination thereof may be used.

[0042] The weight average molecular weight (Mw) of the hydrogenated dicyclopentadiene resin is not particularly limited, but 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 may be 2000 g / mol or less, 1800 g / mol or less, 1600 g / mol or less, or 1500 g / mol or less.

[0043] The polydispersity index (PDI) of the hydrogenated dicyclopentadiene resin may be, for example, 1.0 or more, or 1.3 or more, or 1.5 or more, and may be 3.0 or less, 2.7 or less, or 2.5 or less.

[0044] The weight average molecular weight and polydispersity index of the hydrogenated dicyclopentadiene resin can be measured by gel permeation chromatography (GPC) as exemplified in the following experimental examples.

[0045] The hydrogenated dicyclopentadiene resin may satisfy the oxygen content of 0.1% by weight or more by containing vegetable oil as a comonomer. Specifically, the hydrogenated dicyclopentadiene resin may have an oxygen content of 0.1% by weight or more, 0.3% by weight or more, or 0.4% by weight or more, and may be 5% by weight or less, 3% by weight or less, or 2.7% by weight or less.

[0046] As such, the hydrogenated dicyclopentadiene-based resin according to an embodiment of the present invention exhibits a higher oxygen content than the existing dicyclopentadiene-based resins, and thus may exhibit better solubility in polar solvents and improved compatibility with polar base materials.

[0047] The hydrogenated dicyclopentadiene resin may have a softening point of 70° C. or more, 80° C. or more, or 90° C. or more, and may be 120° C. or less, 110° C. or less, or 105° C. or less. When the hydrogenated dicyclopentadiene resin satisfies the above softening point range, it can be suitably used as a general-purpose hot melt adhesive.

[0048] The hydrogenated dicyclopentadiene resin exhibits excellent physical properties with a loss on drying of 3.5% or less, preferably 3.2% or less, or 3.0% or less. The lower the loss on drying, the better, and theoretically it may be 0%.

[0049] The hydrogenated dicyclopentadiene resin exhibits excellent solubility in solvents.

[0050] Specifically, the hydrogenated dicyclopentadiene resin can satisfy the 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.

[0051] The hydrogenated dicyclopentadiene resin may have a mixed methylcyclohexane-aniline cloud point (MMAP) of 75° C. or less, or 72° C. or less, or 71° C. or less, and may be 50° C. or more, or 60° C. or more.

[0052] The methods for measuring the oxygen content, softening point, loss on drying, diacetone alcohol cloud point, and mixed methylcyclohexane-aniline cloud point of the hydrogenated dicyclopentadiene resin will be specifically described in the following Experimental Examples.

[0053] The above-mentioned hydrogenated dicyclopentadiene resin can be produced by a production method including the steps of: thermally polymerizing a monomer mixture containing dicyclopentadiene and vegetable oil to produce a polymerized dicyclopentadiene resin; and hydrogenating the polymerized dicyclopentadiene resin.

[0054] The vegetable oil contained in the monomer mixture is as described above.

[0055] The monomer mixture may not further contain other monomers other than dicyclopentadiene and vegetable oil. In this case, the content of dicyclopentadiene in the monomer mixture may be 80 to 95% by weight, and the content of vegetable oil may be 5 to 20% by weight. Alternatively, the content of dicyclopentadiene in 100% by weight of the monomer mixture may be 80 to 95% by weight, and the content of vegetable oil may be 10 to 15% by weight.

[0056] Alternatively, the monomer mixture may contain an additional comonomer in addition to dicyclopentadiene and vegetable oil, the additional comonomer used and the amount used being as described above.

[0057] The monomer mixture is dissolved in a solvent, i.e., can be introduced into a thermal polymerization reaction as a monomer composition. The solvent that can be used to prepare the monomer composition is not particularly limited, and can be, for example, at least one selected from the group consisting of pentane, hexane, heptane, nonane, decane, benzene, toluene, and xylene.

[0058] In addition, the monomer composition may further contain additives commonly used in the technical field to which the present invention pertains, such as an antioxidant and a polymerization inhibitor.

[0059] The method of thermally polymerizing the monomer mixture containing dicyclopentadiene and vegetable oil is not particularly limited, but as an example, it can be prepared by a) a first-stage polymerization of thermally polymerizing the monomer mixture in a Continuous Stirred Tank Reactor (CSTR), and b) a second-stage polymerization of thermally polymerizing the reaction product of the first-stage polymerization in a Plug Flow Reactor (PFR). At this time, as described above, the monomer mixture can be used in the form of a monomer composition dissolved in a solvent.

[0060] When the thermal polymerization is carried out in two stages as described above, the heat of the polymerization reaction can be easily controlled, the monomer conversion rate or polymerization rate can be significantly improved, and a dicyclopentadiene-based resin having a narrow molecular weight distribution and uniform physical properties can be provided.

[0061] The reaction temperature (T 1 ) may be 210 to 270° C., or 220 to 270° C. When the reaction is carried out at the above reaction temperatures, the conversion rate or polymerization rate of the monomer is excellent, and the occurrence of side reactions such as crosslinking reactions can be suppressed.

[0062] The reaction pressure in step a) may be 1 to 40 bar, or 5 to 35 bar, or 10 to 30 bar. When the reaction is carried out under the above reaction pressure, the reactivity of the monomer can be increased to a level that does not cause a safety accident.

[0063] The reaction time in step a) may be 10 to 90 minutes, 20 to 80 minutes, or 30 to 70 minutes. If the reaction time is too short, the side reaction caused by mixing the raw materials may not be sufficiently suppressed, and if the reaction time is too long, the productivity of the final resin may be low and the molecular weight distribution may be broad. From this viewpoint, it is preferable to adjust the reaction time to the above-mentioned range.

[0064] The reaction temperature (T 2 ) is the reaction temperature (T 1 ) ±30℃, that is, T 1 -30℃~T 1 +30°C or T 1 -20℃~T 1 +20°C or T 1 -15℃~T 1 The reaction temperature may be +15° C. When the reaction is carried out at the above reaction temperature, side reactions can be suppressed and productivity can be increased.

[0065] In addition, by controlling the temperature difference between steps a) and b) within ±30° C., it is possible to minimize the generation of unreacted oligomers and produce a dicyclopentadiene-based resin having a narrow molecular weight distribution.

[0066] 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 vaporized monomers, and if the pressure is too high, there is a high risk of a safety accident occurring during the process. From this point of view, it is preferable to adjust the reaction pressure to the above-mentioned range.

[0067] The reaction time in the step b) may be 1 to 4 times, 1 to 3 times, or 1 to 2 times the reaction time in the step a). If the reaction time is too short compared to the reaction time in the step a), the reaction may not proceed sufficiently, whereas if the reaction time is too long, a side reaction may occur. From this viewpoint, it is preferable to adjust the reaction time to the above-mentioned range.

[0068] In addition, the internal volume of the PFR used in the stepwise polymerization of b) may be 1 to 3 times, 1 to 2.5 times, or 1 to 2 times the internal volume of the CSTR used in the stepwise polymerization of a) above. If the internal volume of the PFR is too small compared to the internal volume of the CSTR, the polymerization in the PFR may not proceed sufficiently, and a large amount of impurities such as wax may remain, and if the internal volume of the PFR is too large compared to the internal volume of the CSTR, the application effect of the CSTR reactor may be small, and the control of the initial reaction heat may be insufficient, making it difficult to control the reaction temperature. From this point of view, it is preferable to adjust the internal volume of the PFR to the above-mentioned range.

[0069] The hydrogenation reaction or hydrogen addition reaction is not particularly limited and may be carried out by a method known in the technical field to which the present invention belongs. The hydrogenation reaction is a reaction in which hydrogen is added to an unsaturated bond such as a double bond to convert it into a single bond, and a hydrogenated dicyclopentadiene resin can be obtained from a polymerized dicyclopentadiene resin by the hydrogenation reaction.

[0070] The hydrogenation reaction can be carried out by a method known in the art to which the present invention pertains. For example, the obtained polymerized dicyclopentadiene resin can be introduced into a continuous hydrogenation reactor packed with a hydrogenation catalyst to carry out the hydrogenation reaction.

[0071] The hydrogenation catalyst is not particularly limited, and any known hydrogenation catalyst can be used. Specific examples include one or more selected from the group consisting of Ni, Fe, Cu, Co, Mo, Pd, Rh, Pt, Nb, Au, Rd, and Raney Ni.

[0072] In order to improve reactivity, the hydrogenation catalyst can be used in an amount of 0.1 part by weight or more, or 0.3 part by weight or more, or 0.5 part by weight or more and 1.0 part by weight or less, or 0.8 part by weight or less, based on 100 parts by weight of the polymerized dicyclopentadiene resin, but is not limited thereto.

[0073] The conditions for the hydrogenation reaction are not particularly limited, and for example, the reaction can be carried out under a pressure of 50 to 150 bar at a temperature of 150 to 300° C. When the reaction is carried out under such pressure and temperature, destruction of the molecular structure can be prevented.

[0074] Also, hydrogen gas can be continuously introduced during the hydrogenation reaction so that the reaction pressure is maintained constant.

[0075] The hydrogenated dicyclopentadiene resin can be used as a hot melt adhesive or a pressure-reducing adhesive, or can be mixed with one or more base resins selected from the group consisting of ethylene-vinyl acetate resins, polyolefin resins, polyester resins, styrene resins, polyamide resins, and ethylene-acrylic resins to be used as an adhesive or pressure-sensitive adhesive. It can also function as a tackifier or adhesion-imparting resin for inks, paints, road marking paints, etc.

[0076] The functions and effects of the present invention will be described in more detail below through specific examples of the present invention, however, these examples are merely presented as examples of the present invention and do not define the scope of the invention. EXAMPLES

[0077] [Example] Example 1 A monomer composition was prepared by mixing 1425 g of dicyclopentadiene (purity 80%), 75 g of soybean oil, and 1500 g of xylene solvent. The monomer composition was continuously fed into a continuous stirred tank reactor (CSTR, internal volume: 0.416 L) to carry out the first stage polymerization (reaction time: 43 min) at a temperature of 265° C. and a pressure of 25 bar. The reaction product of the first-stage polymerization was continuously fed to a plug flow reactor (PFR, internal volume: 0.590 L) connected to the CSTR, while the second-stage polymerization (reaction time: 67 min) was carried out under conditions of a temperature of 278° C. and a pressure of 25 bar. The product after the polymerization was subjected to reduced pressure at 260° C. for 30 minutes to recover the polymerized dicyclopentadiene resin. The polymerized dicyclopentadiene resin was fed to a 1.5 m long fixed bed reactor filled with a heterogeneous palladium catalyst (0.5 wt% based on 100 wt% polymerized dicyclopentadiene resin), and hydrogenated under the conditions of 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 NlPM to produce a hydrogenated dicyclopentadiene resin.

[0078] Example 2 A polymerized dicyclopentadiene resin and a hydrogenated dicyclopentadiene resin were produced in the same manner as in Example 1, except that 1,350 g of dicyclopentadiene and 150 g of soybean oil were used as monomers, the CSTR reaction temperature was 270°C, and the PFR reaction temperature was 280°C.

[0079] Example 3 A polymerized dicyclopentadiene resin and a hydrogenated dicyclopentadiene resin were produced in the same manner as in Example 1, except that 1275 g of dicyclopentadiene and 225 g of soybean oil were used as monomers, the CSTR reaction temperature was 270°C, and the PFR reaction temperature was 280°C.

[0080] Example 4 A polymerized dicyclopentadiene resin and a hydrogenated dicyclopentadiene resin were produced in the same manner as in Example 1, except that 1200 g of dicyclopentadiene and 300 g of soybean oil were used as monomers, the CSTR reaction temperature was 275°C, and the PFR reaction temperature was 280°C.

[0081] The oxygen content (wt%) of the hydrogenated dicyclopentadiene resins produced in Examples 1 to 4 was measured using an elemental analyzer (EA), and the results are shown in the following Table 1. In addition, infrared spectroscopy (IR) was performed on each of the hydrogenated dicyclopentadiene resins.

[0082] [Table 1]

[0083] As a result of IR analysis of the hydrogenated dicyclopentadiene resins of Examples 1 to 4, a peak derived from the carbonyl group of the vegetable oil was observed at 1745 cm -1 In addition, the actual oxygen content of the hydrogenated dicyclopentadiene resin was measured and found to be similar to the predicted oxygen content calculated from the amount of soybean oil added.

[0084] From the above results, it can be confirmed that vegetable oil (soybean oil) is polymerized with DCPD as a comonomer and is included in the polymer chain.

[0085] Comparative Example 1 Hanwha Solutions' HC-100 was used as Comparative Example 1.

[0086] Comparative Example 2 Hanwha Solutions' HC-120 was used as Comparative Example 2.

[0087] Comparative Example 3 Comparative Example 3 was prepared by blending 95 parts by weight of Hanwha Solution's HC-100 and 5 parts by weight of soybean oil.

[0088] Comparative Example 4 Comparative Example 4 was prepared by blending 85 parts by weight of Hanwha Solution's HC-100 and 15 parts by weight of soybean oil.

[0089] Comparative Example 5 Comparative Example 5 was prepared by blending 75 parts by weight of Hanwha Solution's HC-100 and 25 parts by weight of soybean oil.

[0090] Comparative Example 6 Comparative Example 6 was prepared by blending 95 parts by weight of Hanwha Solution's HC-120 and 5 parts by weight of soybean oil.

[0091] Comparative Example 7 Comparative Example 7 was prepared by blending 85 parts by weight of Hanwha Solution's HC-120 and 15 parts by weight of soybean oil.

[0092] Comparative Example 8 Comparative Example 8 was prepared by blending 75 parts by weight of Hanwha Solution's HC-120 and 25 parts by weight of soybean oil.

[0093] Comparative Example 9 Soybean oil was fed to a 1.5 m long fixed bed reactor packed with a heterogeneous palladium catalyst (0.5 wt% based on 100 wt% soybean oil), and hydrogenation reaction was carried out under the conditions of reaction temperature 250°C, reaction pressure 100 bar, feed flow rate 40 ml / min, and hydrogen flow rate 4 nLPM to produce hydrogenated soybean oil. Comparative Example 9 was prepared by blending 85 parts by weight of Hanwha Solution's HC-100 and 15 parts by weight of the hydrogenated soybean oil.

[0094] Comparative Example 10 Hydrogenated soybean oil was produced in the same manner as in Comparative Example 9, and 75 parts by weight of Hanwha Solution's HC-100 and 25 parts by weight of hydrogenated soybean oil were mixed to prepare Comparative Example 10.

[0095] Comparative Example 11 Hydrogenated soybean oil was produced in the same manner as in Comparative Example 9, and 85 parts by weight of Hanwha Solution's HC-120 and 15 parts by weight of hydrogenated soybean oil were mixed to prepare Comparative Example 11.

[0096] Comparative Example 12 Hydrogenated soybean oil was produced in the same manner as in Comparative Example 9, and 75 parts by weight of Hanwha Solution's HC-120 and 25 parts by weight of hydrogenated soybean oil were mixed to prepare Comparative Example 12.

[0097] Experimental Example (1) Softening point The softening points of the resins were measured twice using an Anton Paar RKA5 instrument according to ASTM E 28, and the average value was calculated and reported in Table 2.

[0098] (2)Molecular weight The weight average molecular weight (Mw), number average molecular weight (Mn), and Z-average molecular weight (Mz) were determined using polystyrene standards by gel permeation chromatography (GPC) (TDA302 manufactured by Viscotek and 1200 series (Pump) manufactured by Agilent). The resin to be measured was dissolved in tetrahydrofuran to a concentration of 4000 ppm, and 100 μl was injected into the GPC. Tetrahydrofuran was used as the mobile phase for GPC, and the flow rate was 1.0 mL / min. The analysis was performed at 35°C. The column was (Agilent PL Mixed C 2set + PL50Å). The detector was an RI detector (Viscotek RI), and the measurements were performed at 35°C. The Mw, Mn, and Mz values ​​were derived using a calibration curve formed after the measurement of polystyrene standards. The molecular weights of the polystyrene standards used were 12 types: 104 / 118 / 236 / 580 / 1480 / 2340 / 2970 / 5030 / 8450 / 10850 / 20650 / 24600. At this time, the PDI (polydispersity index) was calculated by dividing the measured weight average molecular weight by the number average molecular weight.

[0099] (3) Loss on drying 3 g of resin was placed in a heating loss measuring device (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 loss on drying.

[0100] (4) Melt Viscosity (ASTM D 3236) The viscosity of the resin was measured at 180° C. using a Brookfield DV-III viscometer.

[0101] (5) Diacetone Alcohol Cloud Point (DACP) A mixed solution of 5 g of resin, 5 g of xylene, and 5 g of diacetone alcohol was prepared, heated until the solution became transparent, and the DACP was calculated by measuring the temperature at which the solution became cloudy while cooling the solution.

[0102] (6) Mixed Methylcyclohexane-Aniline Cloud Point (MMAP) A mixed solution of 5 g of resin, 5 g of methylcyclohexane, and 10 g of aniline was prepared. The solution was heated until it became transparent, and the MMAP was calculated by measuring the temperature at which the solution became cloudy while cooling the solution.

[0103] (7)Shear Adhesion Failure Temperature(SAFT) A hot melt adhesive (HMA) was prepared by mixing the base resin, each resin of the comparative examples and examples, and Fischer-Tropsch waxes in a ratio of 4:4:2. This was then made into an HMA film of a certain thickness using a Qmesys hot press (QM900A), and the film was cut into a 2.5*2.5cm square and attached to a KLB material type B cardboard to prepare a SAFT measurement sample. The SAFT sample thus prepared was subjected to a SAFT measurement device (Elastocon, ES-07II) with a load of 500 g and the temperature was raised by 1°C every 2 minutes to measure the temperature at which the HMA lost its adhesive force and the sample separated. As the base resin, EVA1529 from Hanwha Solutions was used as the EVA hot melt adhesive, and GA1900 from DOW was used as the mPO hot melt adhesive.

[0104] The SAFT test results for EVA hot melt are shown in Figure 1, and the SAFT test results for mPO hot melt are shown in Figure 2. On the other hand, when mPO was used as the base resin for the resin of Comparative Example 5, the mixture was sticky and in a semi-solid state at room temperature, making it impossible to manufacture an mPO hot melt adhesive.

[0105] [Table 2] [Table 3] [Table 4]

[0106] Referring to Table 1, it can be seen that the hydrogenated dicyclopentadiene resins of Examples 1 to 4 have higher molecular weights than existing petroleum resins due to the use of soybean oil, and have properties such as softening point, loss on drying, DACP, and MMAP that are equivalent to those of commercially available petroleum resins.

[0107] 1 and 2, it can be seen that the EVA hot melt adhesives and mPO hot melt adhesives made with the resins of Examples 1 to 4 exhibit excellent heat resistance equal to or greater than that of existing commercially available petroleum resins. However, it was confirmed that the heat resistance was rather reduced in Comparative Examples 3 to 8, in which soybean oil was not copolymerized but was mixed with commercially available petroleum resin, and Comparative Examples 9 to 12, in which hydrogenated soybean oil was mixed with commercially available petroleum resin.

Claims

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

2. The hydrogenated dicyclopentadiene resin according to claim 1, wherein the vegetable oil is represented by the following chemical formula 1: 【Chemistry 1】 In the above Chemical Formula 1, R １ ~R ３ are each independently an alkyl group having 5 to 20 carbon atoms, １ ~R ３ At least one of the groups contains one or more carbon-carbon double bonds.

3. 3. The hydrogenated dicyclopentadiene resin according to claim 1, wherein the content of the vegetable oil in the monomer mixture is 5% by weight to 20% by weight.

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

1.

5. The hydrogenated dicyclopentadiene resin according to any one of claims 1 to 4, wherein the vegetable oil has a fatty acid content of unsaturated fatty acids of 60% by weight to 90% by weight.

6. The hydrogenated dicyclopentadiene resin according to any one of claims 1 to 5, having an oxygen content of 0.1% by weight to 5% by weight.

7. The hydrogenated dicyclopentadiene resin according to any one of claims 1 to 6, having a softening point of 70°C to 120°C.

8. The hydrogenated dicyclopentadiene resin according to any one of claims 1 to 7, which has a drying loss of 3.5% or less.

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

10. Thermally polymerizing a monomer mixture containing dicyclopentadiene and vegetable oil to produce a polymerized dicyclopentadiene-based resin; and A method for producing a hydrogenated dicyclopentadiene resin, comprising the step of subjecting a polymerized dicyclopentadiene resin to a hydrogenation reaction.

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

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

13. A pressure-sensitive adhesive composition comprising the hydrogenated dicyclopentadiene resin according to any one of claims 1 to 9.

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