WO2017003157A1 - Hydrogenated petroleum resin, and production method and use therefor - Google Patents

Abstract

The present invention relates to a hydrogenated petroleum resin, and to a production method and use therefor, and more specifically relates to a hydrogenated petroleum resin produced by subjecting dicyclopentadiene and an olefinic monomer to thermal polymerisation and then carrying out a hydrogenation reaction, and relates to a production method and use therefor. The hydrogenated petroleum resin has the advantage of being useful in practical applications, since said petroleum resin is produced via thermal polymerisation using inexpensive starting materials and, in contrast to conventional catalyst polymerisation, a catalyst elimination process can be dispensed with. The hydrogenated petroleum resin produced in this way can put to use, for example, as an adhesive agent used in environmentally friendly sanitary articles, as said petroleum resin is outstandingly compatible, has outstanding viscous power and heat resistance and has no smell.

Description

Hydrogenated Petroleum Resin, Manufacturing Method and Use thereof

This application is the Korean Patent Application No. 10-2015-0093774 dated June 30, 2015, the Korean Patent Application No. 10-2015-0191077 dated December 31, 2015, and the Korean Patent Application No. 10- June 27, 2016 Claiming the benefit of priority based on 2016-0080204, all contents disclosed in the literature of the relevant Korean patent application are incorporated as part of this specification.

The present invention relates to a hydrogenated petroleum resin applicable to an adhesive, a method for producing the same, and a use thereof.

Hydrocarbon Resin is a typical tackifier, and is mainly used as a material that gives viscosity and adhesiveness to products such as adhesive tape, paint, ink, rubber, and tires. The properties may be in a variety of forms from liquid of semi-fluid transparent to light yellow and transparent colorless water (Water White) as a liquid or solid thermoplastic at room temperature.

The production of petroleum resins is usually carried out using a catalyst (mainly AlCl ₃ or BF ₃ ), which is a diolefin C ₅ or C ₉ fraction, through polymerization, decatalysis, washing, and resin separation. The improvement of physical properties is attempted by other polymerization systems, such as radical polymerization.

U.S. Patent No. 5,410,004 discloses a petroleum resin prepared by thermal polymerization of dicyclopentadiene (DCPD) and an olefinic modifier in the presence of a strong acid catalyst. However, these petroleum resins contain double bonds and unreacted substances in the molecular structure, and as they are vulnerable to heat or acid, transparency of the petroleum resin color during or after processing decreases, and a bad odor occurs. Accordingly, even when the hydrogenation reaction is performed to remove the double bond, various corrosion problems may occur during the hydrogenation reaction due to the strong acid catalyst. In addition, there is a problem of poor productivity due to low yield.

On the other hand, the petroleum resin can be used as it is after the polymerization, and recently used in the form of hydrogenated petroleum resin prepared by performing an additional hydrogenation process to improve the physical properties.

Hydrogenated petroleum resins are thermoplastic resins made from high-quality unsaturated hydrocarbons in high-temperature pyrolysis oils such as naphtha in petrochemical plants. They are excellent in heat and ultraviolet (UV) light and have properties that provide adhesion. Medical supplies, woodworking supplies, hygienic supplies are used in various ways.

In the case of hydrogenated petroleum resins, it is difficult to completely remove unreacted raw materials, solvents, and low molecular weight oligomers during the manufacturing process. It causes odor, which can also occur when the final product is unpacked. In addition, hydrogenated petroleum resin not only adversely affects the work environment due to its characteristic unpleasant odor when melted at high temperatures, but also when applied to hygiene products, it needs to be used for sensitive and sensitive skin due to odor causing factors. There was a limit to contentment.

Therefore, the demand for odor of petroleum resin used in hygiene products is increasing day by day as the standard of living of consumers increases, so there is an urgent need for the development of technology to improve the odor of petroleum resin.

Accordingly, US Patent No. 5,652,308 discloses a tackifying resin in which a part of C5 monomer is partially replaced with C3 monomer by copolymerizing DCPD prepared from C3 monomer propylene and C5 monomer using a metallocene catalyst. I've done it. However, when the petroleum resin is manufactured by the above method, an expensive metallocene catalyst which is very vulnerable to oxygen and moisture must be used, and thus the process design is complicated and the manufacturing cost is high, and the yield is also very low, which is less than 30%. There was a problem that it is difficult to practically low.

[Preceding technical literature]

[Patent Documents]

US Patent No. 5,410,004 (1995.04.25), Thermal polymerization of dicyclopentadiene

5,652,308 (July 29, 1997), Tackifiers and a process to obtain tackifiers

In order to solve the above problems, the Applicant has conducted a multi-faceted study to produce a hydrogenated petroleum resin by performing a hydrogenation reaction after performing a thermal polymerization process rather than a complex catalytic polymerization, but comonomers in dicyclopentadiene as a raw material When the olefin monomers are used together, the adhesion and heat resistance of the hydrogenated petroleum resin finally obtained are improved and the odor is improved, and when applied to adhesives, the physical properties are also improved, thereby completing the present invention.

Accordingly, it is an object of the present invention to provide a method for producing a hydrogenated petroleum resin that is easy to put into practical use in a simplified process.

In addition, another object of the present invention is to provide a hydrogenated petroleum resin produced by the above-described method is improved physical properties and odor.

Still another object of the present invention is to provide a use of the hydrogenated petroleum resin as an adhesive.

In order to achieve the above object, the present invention provides a hydrogenated petroleum resin comprising a repeating unit represented by the following formula (1) and (2):

(In Formulas 1 and 2, R ₁ is H or a methyl group, R ₂ is an alkyl group of C1 to C18, 0≤m≤10 and 0≤n≤10)

In addition, the present invention comprises the steps of thermally polymerizing a dicyclopentadiene and a C3 to C20 olefin monomer to prepare a petroleum resin; And

It provides a process for producing a hydrogenated petroleum resin comprising the step of performing a hydrogenation reaction by the hydrogenation catalyst of the petroleum resin.

The present invention also provides a use of the hydrogenated petroleum resin in the adhesive composition.

Hydrogenated petroleum resin manufacturing method according to the present invention can solve the supply-demand problem of the raw material by replacing the C3 olefins used as the raw material of the petroleum resin with olefins of 6 to 20 carbon atoms, the heat of polymerization rather than catalytic polymerization By using the polymerization step, the polymerization yield can be greatly improved.

In particular, the hydrogenated petroleum resin produced by the production method of the present invention has not been improved in the conventional petroleum resin to solve the problem that a characteristic unpleasant odor is generated, so that the odor is hardly generated.

In addition, the hydrogenated petroleum resin produced by the above production method has excellent odor, excellent adhesion performance, high softening point, transparent, low molecular weight, excellent color, compatibility with natural rubber or synthetic rubber, etc. It is excellent in that it can be usefully used as an adhesive in various fields, in particular, it can increase the competitiveness in the application to hygiene products.

1 is a schematic diagram illustrating the NMR spectral analysis proposed in the present invention, (a) shows a peak area, and (b) shows a full width at half maximum.

Figure 2 is a flow chart showing a method for producing a hydrogenated petroleum resin proposed in the present invention.

3 is a ¹ H-NMR spectrum of the petroleum resin before hydrogenation of Example 1 according to the present invention.

4 is a ¹ H-NMR spectrum of the petroleum resin after hydrogenation of Example 1 according to the present invention.

5 is a ¹ H-NMR spectrum of the petroleum resin before hydrogenation of Example 5 according to the present invention.

6 is a ¹ H-NMR spectrum of the petroleum resin after hydrogenation of Example 5 according to the present invention.

7 is a ¹ H-NMR spectrum of the petroleum resin before hydrogenation of Example 7 according to the present invention.

8 is a ¹ H-NMR spectrum of the petroleum resin before hydrogenation of Example 8 according to the present invention.

9 is a ¹ H-NMR spectrum of the petroleum resin before hydrogenation of Example 9 according to the present invention.

10 is a ¹ H-NMR spectrum of the petroleum resin before hydrogenation of Comparative Example 1 according to the present invention.

11 is a ¹ H-NMR spectrum of the petroleum resin after hydrogenation of Comparative Example 1 according to the present invention.

The present invention proposes a petroleum resin of a new structure that can be applied to an adhesive or pressure-sensitive adhesive is improved odor.

Hydrogenation Petroleum resin

The hydrogenated petroleum resin according to the present invention is prepared by thermal polymerization of dicyclopentadiene and an olefinic monomer and then produced through a hydrogenation reaction, and includes repeating units represented by the following Chemical Formulas 1 and 2:

 [Formula 1]

[Formula 2]

(In Formulas 1 and 2, R ₁ is H or a methyl group, R ₂ is an alkyl group of C1 to C18, 0≤m≤10 and 0≤n≤10)

Preferably, R ₁ is H, R ₂ may be an alkyl group of C1 to C18.

The alkyl group may be a linear or branched alkyl group, preferably a linear alkyl group. For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, or a tetradecyl group, and among these, a C4 or more alkyl group, a butyl group and a pentyl group , Hexyl group, octyl group, nonyl group, decyl group, dodecyl group, or tetradecyl group is preferable.

Hydrogenated petroleum resin according to the present invention includes the repeating units of Chemical Formulas 1 and 2, but is in a saturated state without a double bond in the molecular structure, and these repeating units have a copolymerized form.

At this time, the form of the copolymer is expressed as described above for convenience, but is not particularly limited in the present invention, random copolymer, alternating copolymer (alternative copolymer), block copolymer (graft), graft copolymer (graft) Various forms such as copolymer and starblock copolymer are possible.

Specifically, the repeating unit of Formula 1 is a repeating unit derived from dicyclopentadiene, Formula 2 is a repeating unit derived by a polymerization reaction of dicyclopentadiene and an olefin monomer which is a comonomer, and an alkyl group at the terminal It has a structure substituted with. The odor of the petroleum resin is improved through the use of an olefin-derived alkyl group constituting the repeating unit of Formula 2. In this case, the petroleum resin may contain 10 to 50 mol%, preferably 10 to 45 mol%, of the alkyl group derived from the olefin in the total petroleum resin. When the content of the alkyl group is less than the above range, it may be difficult to improve the adhesion performance and the odor improvement effect due to the copolymerization with the olefinic monomer. On the contrary, when the content exceeds the above range, the adhesion may be deteriorated.

In addition, the repeating units of Formulas 1 and 2 are preferably present in a predetermined molar ratio, specifically, 40 to 90 mol% of repeating units of Formula 1 and 10 to 60 mol% of repeating units of Formula 2. If the repeating unit of Formula 2 is relatively small, it is not possible to secure an improvement effect such as odor and adhesion performance. On the contrary, when excessively used, the physical properties of the petroleum resin itself decrease, and thus it is appropriately used within the above range.

The structural analysis of the hydrogenated petroleum resin according to the present invention having the above structure may be performed through a ¹ H-NMR analyzer (nuclear magnetic resonance, nuclear magnetic resonance spectroscopy), and the hydrogenated petroleum resin through the peak analysis obtained at this time It can be specified.

¹ H-NMR analysis is an analytical method that tells which atoms the hydrogen atoms in the compound are bound to, and which functional groups they contain. This method can be used for identification and identification of compounds, and can be used for quantitative analysis of mixtures and estimation of molecular structure, as well as for measuring binding state changes.

^{In the 1} H-NMR spectrum, protons (H ⁺ ) having the same relationship in the molecule appear as one peak, and if they are in close proximity with other nuclei, they split and appear as multiplets. In this case, the peak position of the chemical shift (i.e., frequency interval, ppm) is different according to the protons present in the single bond and the double bond (i.e., the unsaturated bond), and the intensity is also different. That is, the chemical shift data can be used to extract information of what kind of protons are present in the molecule, what proportion each proton is present through the intensity, and which protons are adjacent to each other through coupling.

Hydrogenated petroleum resin proposed in the present invention has a repeating structure of Formulas (1) and (2), wherein the repeating unit of Formula (1) consists only of a ring structure derived from dicyclopentadiene, and Formula 2 is derived from an olefin together with the ring structure. The linear structure by the alkyl group of exists simultaneously. As a result, the peak specified by R ₂ in Formula 2 may be confirmed to specify a hydrogenated petroleum resin.

The ¹ H-NMR spectrum of the hydrogenated petroleum resin does not appear as a peak like the compound, but due to the presence of a large number of protons, they influence each other so that peaks exist in a predetermined area as shown in FIGS. 3 to 11. The more conventional proton (hydrogen) makin years the strength, which may be in the R ₂ is long, may be much the content of the repeating units of the formula R ₂ is a substituted 2 days. Accordingly, the present invention specifies the petroleum resin in consideration of both parameters.

When the ¹ H-NMR data of the hydrogenated petroleum resin of the present invention is measured to 0.0 to 9.0 ppm, the peaks associated with the repeating units of Formulas 1 and 2 have a large number of peaks up to 7.5 ppm. The peak of 0.8-1.4 ppm is a proton peak derived from R <_2> , and the other is a proton peak derived from the ring structure of dicyclopentadiene.

The peak of the ¹ H-NMR spectrum is related to the number of protons, and peak analysis between 0.8 and 1.4 ppm is very important to confirm that R ₂ is bonded to the hydrogenated petroleum resin of the present invention. At this time, the peak analysis is divided into a case where the peak area is used as a parameter and a case where the width of the peak is used as a parameter. That is, by analyzing the parameters related to the peak area and the width of the peak, quantitative analysis and qualitative analysis are possible, and the hydrogenation petroleum resin proposed in the present invention can be specified.

1 is a schematic diagram for explaining ¹ H-NMR spectral analysis proposed in the present invention, (a) shows the peak area, and (b) shows the definition of full width at half maximum.

The area of the a to b ppm peaks shown in the present invention of FIG. 1 (a) means the area of the corresponding area when cut in the vertical direction including the base line at a and b ppm points of the X-axis chemical shift. .

In addition, the width of the a 'ppm peak presented in the present invention of Figure 1 (b) is full width at half maximum (FWHM) is the peak including the base line at the a' point of the chemical shift of the X-axis It means the width at the half point (H / 2) of the height (H).

(i) NMR peak area parameter

The hydrogenated petroleum resin of the present invention may be defined by a parameter of the peak area, where the peak area follows the definition as shown in FIG.

Alkyl group of R ₂ in relation to olefin The peak appears in the range of 0.8 to 1.4 ppm, in which the peak is largely divided into two branches. The peak at 0.8 to 1.0 ppm and the peak at 1.0 to 1.4 ppm are related to the amount of R ₂ present, and the ratio of the peak at 0.8 to 1.0 ppm and the peak at 1.0 to 1.4 ppm is R _2. It is a peak which knows what kind of length of carbon number is, that is, the kind of olefin used.

From this information, the hydrogenated petroleum resin according to the present invention can estimate the content of R ^{2 in} the total hydrogenated petroleum resin by measuring the area of the peak obtained after ¹ H-NMR measurement. The area can be easily derived from the NMR spectrometer.

Preferably, the hydrogenated petroleum resin of the present invention has a peak area of 0.8 to 1.0 ppm relative to the peak area of 1.4 to 7.5 ppm in the NMR spectrum obtained after ¹ H-NMR measurement, preferably 0.2 to 0.8, more preferably. It has a range of 0.5 to 0.7 below. The area ratio is related to the content of R ₂ and related to the effect to be obtained by substitution of an alkyl group. That is, when the area ratio is out of the above range, it is not possible to secure effects such as heat resistance improvement and odor improvement of the petroleum resin.

In addition, the hydrogenated petroleum resin of the present invention has a peak area of 1.0 to 1.4 ppm relative to the peak area of 1.4 to 7.5 ppm in the NMR spectrum obtained after ¹ H-NMR measurement, preferably 0.5 to 0.8, more preferably It has a range of 0.6 to 0.7. The area ratio is related to the type of R ₂ and related to the effect to be obtained by substitution of an alkyl group. That is, when the area ratio is out of the above range, it is not possible to secure effects such as heat resistance improvement and odor improvement of the petroleum resin.

In the specific range, the NMR peak area parameter may exist to some extent an alkyl group (R ₂ ) in the hydrogenated petroleum resin, and the type of the olefin monomer used may be predicted. In this case, the area ratio of each peak may satisfy only one or more, and more preferably, all of them may be satisfied.

(ii) NMR peak width parameters

The hydrogenated petroleum resin of the present invention may be defined by a parameter of full width at half maxium (FWHM) of the peak, where the peak area follows the definition as shown in FIG.

As described in the above (i), a peak related to the R ₂ is a peak at 1.0~1.4 ppm related to the peak, the type of R ₂ in 0.8~1.0 ppm related to the amount of appears in 0.8~1.4 ppm, ₂ R It is limited by the full width at half maximum parameter.

Preferably, the full width at half maximum at 0.85 ppm in relation to the substitution degree of R _{2 and} the full width at half maximum at 1.20 ppm in relation to the number of carbon atoms of R ₂ are preferably 0.1 ppm or less, preferably at 0.85 ppm. Below, it is 0.01-0.1 ppm, and the full width at half maximum of a 1.20 ppm peak is 0.4 ppm or less, Preferably it is 0.01-0.4 ppm.

As described in (i), the full width at half maximum parameter is a limited range in which adhesion performance and odor improvement can be achieved through the use of an olefinic monomer. Preferably, the hydrogenated petroleum resin according to the present invention may satisfy only one of the full width at half maximum at 0.85 ppm and 1.20 ppm, more preferably both.

In addition, the hydrogenated petroleum resin according to the present invention has a weight average molecular weight of 500 to 3,000 g / mol, a softening point of 90 to 150 ° C, and a color (APHA color) of 1 to 100. If the weight average molecular weight is less than 500g / mol may be the adhesive strength, if it exceeds 3000g / mol may be insufficient compatibility. If the softening point is less than 90 ℃ adhesive strength may fall, if it exceeds 150 ℃ is not preferable in terms of difficult application of the manufacturing process.

The weight average molecular weight is related to the field of application of hydrogenated petroleum resin, for example, is a range capable of fully exhibiting its function when applied to the field of adhesives presented in the following application part. When the molecular weight is less than the above range, a decrease in adhesion performance occurs, and on the contrary, the above-described range may be exceeded and compatibility with other resins may decrease.

The softening point refers to a temperature at which the softening point is deformed by heat to cause softening. If the softening point is too low when applied to the adhesive field, a problem may occur in that the petroleum resin itself is fused when the petroleum resin is stored, and vice versa. There may be a problem that the adhesiveness of the adhesive is lowered.

In addition, APHA color with respect to color is applied to measure the chromaticity of clear liquid and solid properties, it is usually expressed by subdividing in steps of 1 to 500, the number is correlated with the yellowness index (yellowness index) Has Hydrogenated petroleum resin of the present invention, the value of APHA is 1 to 100, when the value exceeds 100 exhibits an opaque characteristic or the color becomes turbid when mixed with other resins, the value of the product is reduced.

In addition, the compatibility shows how well the resin is miscible with other compositions. In the experimental example of the present invention, the polyolefin rubber and the wax are mixed at a constant ratio, heated to become transparent, and cooled, while the resin composition is clouded at a point where the resin composition becomes cloudy. Compatibility was measured by cloud point. That is, the compatibility means that the room temperature to 150 ℃ means that the hydrogenated petroleum resin and other resin of the present invention can be mixed well at room temperature to 150 ℃.

Hydrogenation Petroleum resin  Manufacturing method

Hydrogenated petroleum resin according to the present invention comprises the steps of preparing a petroleum resin through a thermal polymerization reaction of dicyclopentadiene and olefins of C3 ~ C20; And

The petroleum resin is prepared by performing a hydrogenation reaction with a hydrogenation catalyst to prepare a hydrogenated petroleum resin (see FIG. 2).

Hereinafter, each step will be described in detail.

(S1) Thermal polymerization  Reaction stage

First, a petroleum resin is prepared by thermally polymerizing a C3 to C20 olefin monomer with dicyclopentadiene and a comonomer.

Olefin monomers used as comonomers include olefin compounds up to C20, including C3 olefins, which have conventionally been used as main raw materials for petroleum resins. Preferably, the olefinic monomer may be a linear or branched alpha olefinic monomer.

The above-mentioned alpha olefin monomers, in particular, when linear alpha olefins are used, are more flexible than branched alpha olefins, and have excellent fluidity and structural penetration. Thus, when used as an adhesive or an adhesive, a high wettability to the substrate can be secured to ensure high adhesion. have. In this case, the alpha olefin monomer may be used as one type or a mixture of two or more kinds of the above-mentioned monomers, and is not particularly limited in the present invention.

Available olefinic monomers include ethylene (or ethene), propylene (or propene), 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 Linear alpha-olefins such as dodecene, 1-tetradecene, 1-hexadecene and 1-aitocene, isobutylene, 3-methyl-1butene, 2-methyl-1-butene, 3-methyl-1- Butene, 4-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methyl-1-hexene, dimethyl pentene, diethyl hexene, and the like. Branched alpha-olefins, mixtures thereof and the like can be used alone or in combination, more preferably linear alpha olefins, most preferably 1-hexene, 1-heptene, 1-octene in the liquid state , 1-decene, dodecene and the like are used.

As an example, the reaction of dicyclopentadiene and 1-hexene, which is a C6 olefin, is shown in Scheme 1 below.

Scheme 1

In particular, in the present invention, the polymerization of the dicyclopentadiene and the olefinic monomer is performed through thermal polymerization, not catalytic polymerization.

When a certain level of heat is applied to the dicyclopentadiene and the olefinic monomers, they form radicals themselves, thereby causing an initiation reaction, and producing a petroleum resin through a continuous polymerization reaction. Since the thermal polymerization does not use an initiator, it is possible to solve the problem of increased cost and purity of the petroleum resin.

In addition, the molar ratio of the reactant during the thermal polymerization of the dicyclopentadiene and the olefin monomer is used in a molar ratio of 1: 0.2 to 1: 0.5, preferably 1: 0.25 to 1: 0.45 for the dicyclopentadiene and the olefin monomer. . The molar ratio is related to the physical properties of the finally obtained hydrogenated petroleum resin, and if it is less than the above range, it is difficult to produce a hydrogenated petroleum resin having a desired level of physical property by using too few olefinic monomers. Since the content of the cyclopentadiene is relatively reduced to decrease the physical properties of the final hydrogenated petroleum resin, it is appropriately adjusted within the above range.

In this case, the thermal polymerization is not particularly limited in the present invention, and bulk polymerization and solution polymerization methods may be used. Preferably solution polymerization can be used.

When the solvent is used for solution polymerization, and this step is performed by solution polymerization, dicyclopentadiene is dissolved in a solvent to prepare a dicyclopentadiene solution, and an olefin monomer is added to the obtained dicyclopentadiene solution. After the thermal polymerization is carried out.

In this case, the solvent may be any solvent as long as it can sufficiently dissolve the dicyclopentadiene as described above and is not limited in the present invention. In one example, toluene, methylene chloride, hexane, xylene, trichloro benzene, alkylbenzene, acetonitrile, dimethylformamide, N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, gamma-butyrolactone, furfural , Acetone and a mixed solvent thereof may be selected.

The content of the solvent may be so long as it can dissolve the dicyclopentadiene sufficiently. For example, the solvent is used in the range of 2 to 10 moles with respect to 1 mole of the dicyclopentadiene.

The thermal polymerization is carried out at a temperature at which the initiation and polymerization of the dicyclopentadiene and the olefinic monomer can occur sufficiently, and the temperature can be changed according to the type of the dicyclopentadiene and the olefinic monomer.

Preferably it is carried out at 200 to 320 ℃, more preferably at 250 to 300 ℃, the reaction time is performed for 0.5 to 4 hours, preferably 1 to 2 hours. If the thermal polymerization is performed at 200 ° C. or less than 0.5 hours, the yield may be low, and gel may be formed when thermal polymerization is performed at 320 ° C. or more than 4 hours.

The temperature is directly related to the initiation and polymerization reaction, the initiation does not occur at a temperature below the above range, on the contrary, the decomposition of the dicyclopentadiene or olefin monomers or the formation of gels at the temperature above the above range does not occur. Occurs, and polymerization rate control is not easy.

In addition, the reaction time is related to the yield, and if it is less than the above time, the yield may be low. On the contrary, even if the reaction is carried out for a long time, there is no large increase in yield, so it is uneconomical, and therefore it is appropriately used in the above range.

In particular, the present invention may solve the problem of difficult supply of raw materials of C5 olefins, which were used as main raw materials in conventional petroleum resins by thermal polymerization of dicyclopentadiene and olefinic monomers, and odor which has not been solved in conventional petroleum resins. Can solve the problem. In addition, when the petroleum resin is manufactured by thermal polymerization in this way, the catalyst removal process, which is an essential step in the cationic catalyst process, which is a conventional petroleum resin manufacturing method, may not be required, and the yield may be greatly improved to 90% or more. desirable.

(S2) hydrogenation step

Next, a hydrogenation catalyst is added to the petroleum resin prepared above and a hydrogenation reaction is performed to produce a hydrogenated petroleum resin.

Hydrogenation is a reaction in which hydrogen is added to a double bond in an unsaturated state to form a single bond, and a hydrogenated petroleum resin in which all double bonds are disappeared through a hydrogenation reaction to petroleum resin is produced.

For example, in the following Scheme 2, a step of preparing a hydrogenated petroleum resin prepared from dicyclopentadiene and 1-hexene, which is a C6 olefin, is shown.

Scheme 2

The hydrogenation reaction is carried out by the addition of a hydrogenation catalyst and involves a high exothermic process, which makes the temperature control requirement difficult and maintains high pressure. Preferably, the hydrogenation reaction is carried out at 150 to 300 ℃ under a pressure of 50 to 150 bar. If the temperature and pressure are less than the above range, the hydrogenation reaction may not be sufficiently performed. On the contrary, if the temperature and the pressure exceed the above range, the molecular structure may be destroyed by the severe reaction conditions, and thus, appropriately controlled within the above range.

The hydrogenation catalyst used at this time is not specifically limited in this invention, Any known hydrogenation catalyst can be used. For example, the hydrogenation catalyst may be one selected from the group consisting of Ni, Fe, Cu, Co, Mo, Pd, Rh, Pt, Nb, Au, Rd, Raney Ni, and combinations thereof. Use Pd.

The hydrogenation catalyst is used in a molar ratio of 0.001 to 0.5, preferably 0.05 to 0.2, per mole of dicyclopentadiene. If less than 0.001 mole is used per 1 mole of dicyclopentadiene, the reactivity may be insufficient, and if it exceeds 0.5 mole, there is a disadvantage that it is not economical to use a large amount of catalyst.

The production method of hydrogenated petroleum resin according to the present invention can be produced with a high yield of hydrogenated petroleum resin through thermal polymerization, can simplify the process and reduce the cost and can be easily applied to the commercialization process.

Specifically, there is no need to use expensive catalysts used in the conventional catalyst polymerization, and the catalyst removal process is basically excluded after the completion of the reaction, thereby simplifying the process itself and reducing the device cost and the process cost, thereby improving the production process. Can be.

The manufacturing method according to the present invention described above can produce a petroleum resin having a significantly improved odor with a high yield of 90% or more.

Usage

The petroleum resin prepared in the present invention can impart point and adhesive performance to hot melt adhesives, pressure-sensitive adhesives, inks, paints, road marking paints, and the like, and is blended with various resins such as natural rubber and synthetic rubber to form an adhesive. It can be usefully used.

In addition, the present invention is a petroleum resin comprising a repeating unit represented by the formula 1 and the repeating unit represented by the formula (2); Styrenic block copolymers such as styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, polyethylene, polypropylene, At least one polymer selected from ethylene based poly olefin block copolymers such as ethylene vinyl acetate and propylene-ethylene copolymers; And an adhesive selected from the group consisting of synthetic waxes such as paraffin wax, microstalin wax, animal natural waxes, vegetable natural waxes, aromatic oils, naphthenic oils and paraffinic oils.

 The softening point of the adhesive prepared from the adhesive composition is 50 to 150 ℃, the melt viscosity is characterized in that 300 cps to 10,000 cps at 160 ℃, 200 cps to 8,000 cps at 180 ℃.

If the softening point of the adhesive is less than 50 ℃ may be inferior to the adhesive force, if it exceeds 150 ℃ in terms of difficulty in the application of the manufacturing process is not preferable.

In addition, the melt viscosity may be inferior in workability when exceeding 10,000 cps at 160 ° C, may be inferior in adhesive strength when less than 300 cps, and may be inferior in processability when it exceeds 8,000 cps at 180 ° C, and may be inferior in adhesiveness below 200 cps.

The adhesive prepared from the adhesive composition may be used as a hot melt adhesive (HMA) or a pressure sensitive adhesive (HMPSA).

Hot melt adhesives have excellent properties as adhesives with compatibility of 100 ℃ or less, Hardness 30 to 90 ℃, Open time 5 seconds to 30 seconds, Set time 0.1 seconds to 5 seconds. It can be seen that.

In the case of the pressure-sensitive adhesive, the ball tack method is 40 cm or less in the initial stage, 40 cm or less after aging, and is 500 gf / in or more in the peel strength method, 500 gf / in or more after the aging, and 30 in the holding power method. min or more, 30 min or more after aging, the initial 40 ℃ or more, 40 ℃ or more after aging in the SAFT method, it can be seen that it has excellent physical properties as a pressure-sensitive adhesive.

As described above, the adhesive according to the present invention is a hydrogenated petroleum resin which is free of double bonds by hydrogenation and is produced by thermal polymerization, so that unreacted raw materials, solvents and low molecular weight oligomers do not occur. Unpleasant smell (odor) is improved. Such adhesives can be preferably used in all fields requiring the use of adhesives, especially hot melt pressure-sensitive adhesives or adhesives for hygiene products in contact with the human body such as diapers, sanitary napkins and adult diapers.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are not intended to limit the scope of the present invention, which will be construed as to help the understanding of the present invention.

EXAMPLE

Example  One

In a 1 L autoclave, a mixture of 1.5 mol of dicyclopentadiene (DCPD) dissolved in 4 mol of toluene as a solvent was prepared, 0.5 mol of 1-hexene was added thereto, and after the reactor was joined, the reaction temperature was maintained at 270 ° C. The reaction was terminated after the thermal polymerization reaction for a time. After the reaction was completed, the resulting petroleum resin was distilled at 240 ° C. for 5 minutes to recover the unreacted fraction, and 55 g of the remaining petroleum resin was obtained. Toluene was added 1.5 times as a hydrogenated solvent to 55 g of the obtained petroleum resin to completely dissolve it, and then 1 L autoclave was added thereto.

0.2 mol of a palladium catalyst was added thereto, and after the reactor was fastened, a hydrogenation reaction was performed at a hydrogen pressure of 80 bar and a temperature of 230 ° C. for 90 minutes. After the reaction was completed, the reaction product was distilled at 260 DEG C for 10 minutes in a vacuum of 10 torr to prepare 50 g of hydrogenated petroleum resin. Each detailed component was prepared in the content shown in Table 1.

Whether the petroleum resin before hydrogenation and the petroleum resin after hydrogenation were polymerized above was confirmed by measuring by using a nuclear magnetic resonance spectrometer (500 NMR of Bruke, 14.1 telsa), and the results are shown in FIGS. 3 and 4. Same as That is, the ¹ H-NMR spectrum result confirming the structure of the petroleum resin before hydrogenation is a peak indicating a methyl group (-CH ₃ ) derived from 1-hexene between 0.85 and 0.95 ppm in the ¹ H-NMR measurement as shown in FIG. 3. It can be seen that the peak increases, and at the same time, the peak indicating the <-CH _2- > chain of 1-hexene between 1.20 and 1.30 ppm increases, indicating that DCPD and 1-hexene are copolymerized.

In addition, the ¹ H-NMR spectrum results confirming the structure of the petroleum resin after hydrogenation are as shown in Fig. 4, which shows peaks representing 1-hexene methyl groups (-CH ₃ ) between 0.85 and 0.95 ppm in the ¹ H-NMR measurement. Peak) is vaporized, and at the same time, peaks indicating <-CH _2- > chains of 1-hexene between 1.20 and 1.30 ppm increase, indicating that DCPD and 1-hexene are copolymerized resins, and at the same time 4.9 to 6.5 ppm It can be seen that the hydrogenation is completed by confirming that the double bond peak between is completely removed.

At this time, in the method of measuring the ¹ H-NMR spectrum, the peak between 0.85 and 0.95 ppm is the methyl group of the olefin, and the peak between 1.20 and 1.30 ppm is the peak of the <-CH _2- > chain of the olefin and is between 4.9 and 6.5 ppm. The peak is a peak of a double bond of dicyclopentadiene, and as shown in the results of FIGS. 3 and 4, the value of each peak is compared to determine whether DCPD and olefin (Olefin) are copolymerized and whether the hydrogenation reaction proceeds. You can check it.

Example  2 to 14

Petroleum resins of Examples 2 to 14 were prepared by the method of Example 1, according to the conditions shown in Table 1 below.

At this time, the ¹ H-NMR spectrum results of the petroleum resin before hydrogenation and the petroleum resin after hydrogenation are shown in FIGS. 5 (before hydrogenation) and FIG. 6 (after hydrogenation), respectively. ¹ H-NMR spectrum result of a petroleum resin prior to the manufacture hydrogenation is showed in ¹ H-NMR spectrum result 8 of a petroleum resin prior to the hydrogenation of example 8, it showed in Figure 7, hydrogenation of example 9 ¹ H-NMR spectrum results of the entire petroleum resin are shown in FIG. 9.

Comparative example  One

2.0 mol of dicyclopentadiene (DCPD) was dissolved in 4 mol of toluene as a solvent in a 1 L autoclave. After completion of the reactor, the reaction temperature was maintained at 270 ° C. and the reaction was terminated after 2 hours. After the reaction was completed, the produced petroleum resin was distilled at 240 ° C. for 5 minutes to recover the unreacted fraction, and 57 g of the remaining petroleum resin was obtained.

Toluene was added 1.5 times as a hydrogenation solvent to 57 g of the obtained petroleum resin to completely dissolve and 1 L autoclave. 0.2 mol of a palladium catalyst was added thereto, and after the reactor was fastened, hydrogenation was performed at a hydrogen pressure of 80 bar and a temperature of 230 ° C. for 90 minutes. After the reaction was completed, the reaction product was distilled at 260 ° C. for 10 minutes in a vacuum of 10 torr to prepare 53 g of hydrogenated petroleum resin. Each detailed component was prepared in the content shown in Table 1.

Whether the petroleum resin before hydrogenation and the petroleum resin after hydrogenation were polymerized above was confirmed by measuring by using a nuclear magnetic resonance spectrometer (500 NMR of Bruke, 14.1 telsa), and the results are shown in FIGS. 10 and 11. Shown in

Comparative example  2, 3

Petroleum resins of Comparative Examples 2 and 3 were prepared by the method of Comparative Example 1 according to the conditions shown in Table 1 below.

Comparative example  4, 5: catalytic polymerization

Dicyclopentadiene (DCPD) was dissolved in 500 ml of toluene as a solvent in a 1 L autoclave, and tricyclodecene (TCDE) as a polymerization regulator was added thereto. An initiator was added thereto, and after the reactor was fastened, olefin was added, a catalyst was added to the mixture, and the reaction was performed. The reaction temperature was maintained at 40 ° C and the reaction was terminated after 2 hours. After completion of the reaction, the resulting petroleum resin was mixed with 300 g of water to separate the catalyst, and then distilled at 240 ° C. for 5 minutes to recover the unreacted oil to obtain the remaining petroleum resin.

Toluene was added 1.5 times as a hydrogenated solvent to 300 g of the obtained petroleum resin to completely dissolve and 1 L autoclave. 60 g of a palladium catalyst was added thereto, and hydrogenation was carried out for 90 minutes at a hydrogen pressure of 80 bar and a temperature of 230 ° C. after the fastening. After the reaction was completed, the reaction product was distilled at 250 ℃ for 5 minutes in a vacuum of 5torr to prepare a hydrogenated petroleum resin. Each detailed component was prepared in the content shown in Table 1.

[ Experimental Example ]

< Experimental Example  1: Resin Characterization Method>

1) yield

The yield is calculated | required by the following formula.

Yield (%) = Resin obtained (g) / Monomer input (g) * 100

(2) softening point

The softening point was measured by Ring and ball softening method (ASTM E 28). Melt the resin into a ring-shaped mold, place it in a beaker containing glycerin, place the ball on the ring containing the resin, and raise the temperature by 2.5 ℃ per minute to raise the temperature (softening point) when the ball melts. It measured and described in Table 3.

(3) molecular weight

Polystyrene reduced weight average molecular weight and number average molecular weight were measured by gel permeation chromatography (GPC) (PL GPC-220). Hydrogenated petroleum resin to be measured was dissolved in 1,2,4-trichlorobenzene so as to have a concentration of 0.34% by weight, and 288 µl was injected into GPC. The mobile phase of GPC used 1,2,4-trichlorobenzene and flowed in at a flow rate of 1 mL / min, the analysis was performed at 130 ℃. The column was connected in series with two Guard columns and one PL 5μl mixed-D. The detector was measured using a differential scanning calorimeter at a temperature of 10 ° C./min to 250 ° C., analyzed in N ₂ atmosphere, and analyzed to 2nd scan.

Mw shown in Table 3 means a weight average molecular weight, MWD means Mw / Mn.

(4) hydrogenation Petroleum resin  Content analysis of olefins in

The content (mol%) of olefins in hydrogenated petroleum resin can be analyzed from ¹ H-NMR spectra through nuclear magnetic resonance spectroscopy (Bruker 500NMR, 14.1 telsa).

(5) color ( APHA )

Color measurements were measured by ASTM D1544. Specifically, 10.0 g of hydrogenated petroleum resin was dissolved in 10.0 g of toluene, and then the cross section was placed in a rectangular quartz cell (5 cm wide, 4 cm long and 50 mm long). The cell was mounted with PFX195 COLORMETER and operated to measure APHA color.

(6) specific gravity

Specific gravity was measured by ASTM D71. Specifically, 5 g of hydrogenated petroleum resin is dissolved in a hotplate at 200 ° C., poured into a sphere-shaped ring, and only the hydrogenated petroleum resin in a spherical form is removed from the ring and placed in a hydrometer (QUALITEST: Densimeter SD-200L) to measure specific gravity. It was.

(7) odor intensity

The petroleum resin was evaluated for odor intensity for five men and women. 10 g of petroleum resin is placed in a 100 ml beaker and placed in an oven at 180 ° C. for 30 minutes. Remove the beaker from hot state and evaluate the odor generated from petroleum resin. The odor intensity evaluation method directly smelled and classified by the values in the classification table of the following Table 2 to give a score from 0 to 5 points to measure the average score.

<Result Evaluation of Resin Characteristics>

The results measured by the above method are shown in Table 3 below.

As shown in Table 3, it can be confirmed that Examples 1 to 9 were prepared in a yield of 90% or more. In addition, it can be seen that the odor is significantly improved when the compositions of all the examples are compared with the compositions of the comparative examples. Among them, it can be seen that excellent results are obtained when the C4 or more alkyl group is substituted as in Examples 1 to 12.

In addition, in the case of Comparative Examples 4 and 5 were polymerized through a cationic catalyst, it can be seen that the yield is significantly reduced, the molecular weight and the molecular weight distribution is quite high.

Therefore, the method of preparing petroleum resin according to the present invention is different from the hydrogenation reaction after polymerization through a low temperature polymerization of about 40 ° C. in the presence of a cationic catalyst, which is a conventional method for producing petroleum resin, and high temperature heat of about 200 to 300 ° C. without a catalyst. By polymerizing through hydrogenation to perform hydrogenation, a separate catalyst removal process is not required, thereby increasing the yield to significantly increase productivity, and at the same time, it can be seen that the level of odor is almost equal or even better.

In addition, the results obtained by calculating the area ratio of each peak from the ¹ H-NMR spectrum results of Examples 1, 5 and Comparative Example 1 are shown in Table 4.

A1: 0.8-1.0 ppm peak area in ¹ H-NMR spectrum

A2: 1.0 to 1.4 ppm peak area in the ¹ H-NMR spectrum

A3: 1.4 to 7.5 ppm peak area in the ¹ H-NMR spectrum

< Experimental Example  2: Preparation of Adhesives and Measurement of Properties>

In order to confirm the performance of the hydrogenated petroleum resin produced as an adhesive in the present invention was carried out as follows.

< Method of evaluating the performance of the adhesive >

The compatibility, viscosity, and softening point used the method used by the resin characteristic evaluation method.

(1) Hardness (A)

It was measured using a Shore A durometer of 124 ASTM standard. The sample to be measured was laid on a flat surface and the measured value was recorded by puncturing the sample with a sharp part of the hardness tester.

(2) Open time

Open time was measured by JIT's hot melt tester. After applying a certain amount of adhesive to a cardboard 5 cm x 5 cm, and then attached to the cardboard 5 cm x 10 cm, the strength was increased from 0 to 5 seconds to record the force when the cardboard is detached. When the graph was drawn, the time at which it began to descend rapidly was recorded.

(3) Set time

Set time was measured by JIT's hot melt tester. After applying a certain amount of adhesive on a cardboard of 5 cm x 5 cm, after attaching a cardboard of 5 cm x 10 cm length was increased from 0 to 0.5 seconds to record the force when the cardboard is detached. When the graph was drawn, the time when the value of the Y-axis force began to become constant was recorded.

(4) Peel strength

Measurement was made using a UTM instrument. A tape was prepared by first applying a sample (adhesive) to the PET film to a thickness of 25 micrometers. It was attached to the SUS-304 steel plate. The portion where the PET film was attached was mounted on the UTM grip and measured at a speed of 30 mm / min. At this time, the value input to the UTM device means the adhesive force (kgf / in).

(5) Adhesion Evaluation: Ball Tack

Adhesion was evaluated by the ASTM D3121 method.

The test piece tape coated with 20-30 micrometers of adhesive was cut into 10 cm width and 50 cm length. The ball tack tester (JIS Z0237) was placed at one end and the angle was set at a standard inclination angle of 30 degrees, and the steel ball No. 9 was rolled on it to measure the distance rolled. The less the ball rolls, the better the tack.

(6) Adhesion Evaluation: Holding power

Adhesion was evaluated by the ASTM D3330 method.

The test piece tape coated with 20-30 micrometers of adhesive was cut out by 2 inches wide by 6 inches long. The test piece was attached to a release paper, made into 1 inch wide and 2 inch long, and then attached to the cleaned SUS 304 steel sheet. (At this time, the non-stick test piece was attached to be about 2 cm or more. Roll was compressed by reciprocating once). The test piece which did not adhere to the SUS 304 steel plate was cut with scissors so that it might become about 2 cm. A test piece that did not adhere to the SUS 304 steel sheet was inserted into a ring for measuring Cohesion and bonded to the test piece that passed. The front and back of the SUS 304 steel sheet to which the test piece is bonded with a fixing scotch tape were attached to each of the front and back in parallel, and two stamps were fixed between the ring for cohesion measurement and the SUS304 steel plate with a stamper. The remaining attached test piece was cut so that the test piece adhered to the SUS 304 steel plate by 1 inch in width and 1 inch in length.

It was hung on the SUS plate holder in the Shear test oven. A 1 kg weight was hung on the holding power measurement hook attached to the specimen. Added time to add to the timer.

(7) Adhesion Evaluation: SAFT

Adhesion was evaluated by the ASTM D3654 method.

The specimen tape with 20-30 microns of adhesive was cut by 2 inches * 6 inches. The test piece was attached to a release paper, made into 1 inch wide and 2 inch long, and then attached to the cleaned SUS 304 steel sheet. (At this time, the non-stick test piece was attached to be about 2 cm or more. Roll was compressed by reciprocating once). The test piece which did not adhere to the SUS 304 steel plate was cut | disconnected with the scissors so that it might become about 2 cm. A test piece that did not adhere to the SUS 304 steel sheet was inserted into a ring for measuring Cohesion and bonded to the test piece that passed. The SUS 304 was fixed to the front and back of each of the SUS 304 steel sheet to which the test piece was bonded with a fixing scotch tape, and two pieces were placed in parallel between the hoop 304 and the SUS304 steel sheet. The remaining attached test piece was cut so that the test piece adhered to the SUS 304 steel plate by 1 inch in width and 1 inch in length.

 It was hung on the SUS plate holder in the Shear test oven. A 1 kg weight was hung on the holding power measurement hook attached to the specimen. And oven temperature was raised to 0.4 degree / min, and the temperature at the time of further falling was recorded.

(8) heat resistance evaluation

Aging of the sample in a test tube 10g and 180 ℃ oven. After 24 hours, it was evaluated on a Gardner color scale. Gardner color has 18 color levels and recorded the color of the color closest to the naked eye.

(9) Viscosity

Brookfield viscometer was used. A HT-2DB chamber was used and a sample of 10.5 was injected into Spindle No. 27. After heating up to the desired temperature for measurement, it had a stabilization time for 30 minutes. Viscosity values were recorded when the Torque had a 50% value, starting with 0.5 the stirring shaft RPM.

(10) Softening point

The softening point was measured by Ring and ball softening method (ASTM E 28). Melt the resin into a ring-shaped mold, place it in a beaker containing glycerin, place the ball on the ring containing the resin, and raise the temperature by 2.5 ℃ per minute to raise the temperature (softening point) when the ball melts. It measured and described in Table 3.

Experimental Example  3: me-PP based Hot melt  Pressure Sensitive Adhesive (me-PP based HMPSA , Preparation of Adhesives A) and Measurement of Properties

Dow Chemical's Infuse 9807 (metallocene catalyzed ethylene based poly olefin block copolymer) 20wt% as polymer, KL-240 (Michang Petrochemical) 20wt% as oil and 60wt% petroleum resin utilized in Examples and Comparative Examples Example 2, 6, 8, Example 13, and Comparative Example 1, which were mixed with 0.75 parts of antioxidant (Songno Industrial Co., Ltd. Songnox 1010) to 100 parts by weight of a me-PE pressure-sensitive adhesive (HMPSA). Adhesive A (HMPSA) was prepared.

The production conditions were prepared by putting the raw materials of the four kinds (petroleum resin, polymer, oil, antioxidant) in a 100ml beaker and stirred at 180 ° C. for 4 hours, and detailed weight parts and characteristics evaluation results are shown in Table 5. At this time, * Aged in the following table shows the result of measurement after leaving each sample at 70 ° C. for 3 days.

Experimental Example  4: me- PE  based Hot melt  Pressure Sensitive Adhesive (me- PE  based HMPSA , Measurement of physical properties of adhesive B)

20 wt% of Exxonmobil chemical Vistamaxx 6202 (metallocene catalyzed poly propylene) and 20 wt% of Evonik Vestoplast 703 (Amorphous propylene-ethylene copolymer), 22.5 wt% of KL-240 Unchanged Petrochemical Co., Ltd. With respect to 100 parts by weight of the mixture containing 50% by weight of the petroleum resin utilized, a mixture of 0.75 parts by weight of an antioxidant (Songnox 1010, Songwon Industrial Co., Ltd.) was used as an HMPSA adhesive (me-PP based HMPSA). Examples 2, 6, 8, 9, Adhesive B (HMPSA) of 13 and Comparative Example 1 was prepared.

The production conditions were prepared by putting the raw materials of the four kinds (petroleum resin, polymer, oil, antioxidant) in a 100ml beaker and stirring at 180 ° C. for 4 hours, and detailed weight parts and characteristics evaluation results are shown in Table 6.

* Aged in the above table shows the result of measurement after leaving each sample at 70 ℃ for 3 days.

Experimental Example  5: SIS Hot melt  Pressure sensitive adhesive (SIS based HMPSA , Preparation of Adhesives C) and Measurement of Properties

It contains 25 wt% of Kraton Polymer's SIS D-1161 (Styrene-Isoprene-Styrene Block Colpolymer), 18 wt% of KL-240 (Michang Petrochemical Co., Ltd.), and 57 wt% of petroleum resin used in Examples and Comparative Examples. 0.75 parts by weight of antioxidant Songwon Industrial Co., Ltd. Songnox 1010) was added to 100 parts by weight of the mixture to prepare Examples 2, 6, 8, 9, 13, and Adhesive C (HMPSA) of Comparative Example 1, which was HMPSA adhesive (SIS based HMPSA). Prepared.

The production conditions were prepared by putting the raw materials of the four kinds (petroleum resin, polymer, oil, antioxidant) in a 100ml beaker and stirred at 180 ° C. for 4 hours, and detailed weight parts and characteristics evaluation results are shown in Table 7.

Experimental Example  6: me- PE  based Hot melt  Adhesive (me- PE  based HMA , Measurement of physical properties of adhesive D)

40 wt% of Dow Chemical's Affinity 1950GA (metallocene catalyzed poly ethylene) as a polymer, 20 wt% of Sasol C-80 (Sasol) as a wax, and 40 wt% of petroleum resin used in Examples and Comparative Examples Adhesives D (HMA) of Examples 2, 6, 7, 8, 13, Comparative Examples 1, 2 and 4, which are HMA), were prepared.

The production conditions were prepared by putting the four kinds of raw materials in a 100ml beaker and stirred for 1 hour at 180 ℃, detailed weight parts and characteristics evaluation results are shown in Table 8.

Experimental Example  7: EVA Hot melt  glue( EVA  based HMA , Measurement of physical properties of adhesive E)

40 wt% of Arkema EVA 28/400 (Ethylene Vinyl Acetate, VA contents 28%, MI 400) as a polymer, 20 wt% of Sasol C-80 (Sasol) as a wax, and 40 wt% of petroleum resin used in Examples and Comparative Examples. Adhesive E (HMA) of Examples 2, 6, 7, 8, 13, Comparative Examples 1, 2, and 4, which were mixed and HMA adhesives (EVA based HMA), were prepared.

The production conditions were prepared by putting the four kinds of raw materials in a 100ml beaker and stirred for 1 hour at 180 ℃, the detailed weight parts and characteristics evaluation results are shown in Table 9.

Experimental Example  8: APAO Hot melt  glue( EVA  based HMA , Measurement of physical properties of adhesive F)

Evonik's Vestoplast 703 (Amorphous propylene-ethylene copolymer) 40wt% as a polymer, Sasol C-80 (Sasol) 20wt% as a wax and 40wt% petroleum resin used in Examples and Comparative Examples Adhesives F (HMA) of Phosphorous Examples 2, 6, 7, 8, 13 and Comparative Examples 1, 2 and 4 were prepared.

The production conditions were prepared by putting the four kinds of raw materials in a 100ml beaker and stirred at 180 ° C. for 1 hour, and detailed weight parts and characteristics evaluation results are shown in Table 10 below.

Through the adhesives A to F, it can be seen that the adhesive of the present invention increases adhesive strength, improves odor, and improves heat resistance.

As described above in detail specific parts of the present invention, for those skilled in the art, these specific descriptions are merely preferred embodiments, and the scope of the present invention is not limited thereto. Thus, the substantial scope of the present invention will be defined by the claims of the appended claims and their equivalents.

Claims (21)

Hydrogenated petroleum resin, characterized in that it comprises a repeating unit represented by the formula (1) and (2): [Formula 1]

[Formula 2]

(In the above formulas (1) and (2), R ₁ is H or a methyl group, R ₂ is an alkyl group of C1 to C18, and 0 ≦ m ≦ 10 and 0 ≦ n ≦ 10.) The method of claim 1, R ₁ is H, and R ₂ is methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl or tetradecyl group Suzy. The method of claim 1, R ₁ is H, and R ₂ is a butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, or tetradecyl group, characterized in that the hydrogenated petroleum resin. The method of claim 1, The hydrogenated petroleum resin is a hydrogenated petroleum resin, characterized in that it comprises 60 to 90 mol% of repeating units of Formula 1 and 10 to 40 mol% of repeating units of Formula 2. The method of claim 1, The hydrogenated petroleum resin is hydrogenated petroleum resin, characterized in that the peak area of 0.8 to 1.0 ppm relative to the peak area of 1.4 to 7.5 ppm in the NMR spectrum obtained after ¹ H-NMR measurement. The method of claim 1, The hydrogenated petroleum resin is hydrogenated petroleum resin, characterized in that the peak area of 1.0 to 1.4 ppm relative to the peak area of 1.4 to 7.5 ppm in the NMR spectrum obtained after the ¹ H-NMR measurement. The method of claim 1, The hydrogenated petroleum resin has a peak area of 0.8 to 1.0 ppm relative to the peak area of 1.4 to 7.5 ppm and 1.0 to 1.4 ppm relative to the peak area of 1.4 to 7.5 ppm in the NMR spectrum obtained after ¹ H-NMR measurement. Hydrogenated petroleum resin, characterized in that the peak area is 0.5 to 0.8. The method of claim 1, The hydrogenated petroleum resin in the NMR spectrum obtained after ¹ H-NMR measurement, A hydrogenated petroleum resin, characterized in that the full width at half maximum (FWHM) is 0.8 ppm or less. The method of claim 1, The hydrogenated petroleum resin in the NMR spectrum obtained after ¹ H-NMR measurement, Hydrogenated petroleum resin, characterized in that the full width at half maximum of the 1.20 ppm peak is 0.4 ppm or less. The method of claim 1, The hydrogenated petroleum resin in the NMR spectrum obtained after ¹ H-NMR measurement, A hydrogenated petroleum resin, characterized in that the full width at half maximum at the 0.85 ppm peak is 0.01 to 0.1 ppm and the full width at half maximum of the 1.20 ppm peak is 0.01 to 0.4 ppm. The method of claim 1, The hydrogenated petroleum resin is a hydrogenated petroleum resin, characterized in that the weight average molecular weight of 500 ~ 3,000 g / mol, a softening point of 90 ~ 150 ℃, the color (APHA color) 1 ~ 100. Preparing a petroleum resin by thermally polymerizing dicyclopentadiene and a C3 to C20 olefin monomer; And Process for producing a hydrogenated petroleum resin comprising the step of performing a hydrogenation reaction by the hydrogenation catalyst of the petroleum resin. The method of claim 12, The olefin monomer is a method for producing hydrogenated petroleum resin, characterized in that the linear or branched alpha olefin monomer. The method of claim 13, The linear alpha olefin monomers are propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1 -Method for producing hydrogenated petroleum resin, characterized in that the one selected from the group consisting of hexadecene, 1- itocene and combinations thereof. The method of claim 13, The branched alpha olefin monomer is isobutylene, 3-methyl-1 butene, 2-methyl-1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene , 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methyl-1-hexene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl A method for producing hydrogenated petroleum resin, characterized in that one kind selected from the group consisting of -1-pentene and combinations thereof. The method of claim 12, The thermal polymerization reaction method for producing a hydrogenated petroleum resin, characterized in that carried out at 200 ~ 320 ℃. The method of claim 12, The hydrogenation catalyst is a method for producing hydrogenated petroleum resin, characterized in that at least one selected from the group consisting of nickel, palladium, cobalt, platinum and rhodium catalyst. The method of claim 12, The hydrogenation reaction is a method of producing a hydrogenated petroleum resin, characterized in that carried out at a temperature of 150 to 300 ℃ under a pressure of 50 to 150 bar. An adhesive composition comprising the hydrogenated petroleum resin according to any one of claims 1 to 11. The method of claim 19, The adhesive composition is a adhesive composition comprising any one or more of a base polymer, wax, oil. The method of claim 19, The adhesive composition has a softening point of 50 to 150 ° C, a melt viscosity of 300 to 10,000 cps at 160 ° C, 200 to 8,000 cps at 180 ° C.

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