KR20170003425A - Hydrogenated petroleum resin, preparation method thereof, and the use of the same - Google Patents

Abstract

The present invention relates to a hydrogenated petroleum resin, a production method thereof, and a use thereof. More specifically, the present invention relates to a hydrogenated petroleum resin which is obtained by thermopolymerizing dicyclopentadiene and an olefin-based monomer and then carrying out a hydrogenation reaction. The present invention further relates to a production method thereof and a use thereof. According to the present invention, the hydrogenated petroleum resin is produced by undergoing thermopolymerization using inexpensive raw materials, and does not require a process for removing catalysts unlike existing catalytic polymerization, thereby enabling commercialization. Additionally, the hydrogenated petroleum resin produced thereby can be commercialized, and exhibits outstanding adhesiveness and heat resistance while not producing odor. Therefore, the hydrogenated petroleum resin can be applied to adhesives used in eco-friendly hygiene products.

Description

Hydrogenated petroleum resin, preparation method and use thereof, and use thereof

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 point-and-stick material for products such as adhesive tape, paint, ink, rubber, and tire. The properties can be various forms ranging from liquids of transparent semi-liquid bodies to liquids or solid thermoplastic resins at room temperature, to quasi-yellow and transparent water-white solids.

The production of petroleum resin is usually carried out by a process such as de-catalysis, washing and resin separation after polymerization of a diolefin C ₅ or C ₉ oil with a catalyst (mainly AlCl ₃ or BF ₃ ) Or by other polymerization methods such as radical polymerization.

U.S. Patent No. 5,410,004 discloses a petroleum resin prepared by thermally polymerizing dicyclopentadiene (DCPD) and an olefinic modifier in the presence of a strong acid catalyst. However, these petroleum resins contain double bonds and unreacted materials in the molecular structure, and as they become vulnerable to heat or acid, the transparency of the petroleum resin color during processing or after processing is lowered, resulting in serious odor problems. Therefore, even if the hydrogenation reaction is carried out to eliminate the double bond, it is difficult to react because the strong acid catalyst may cause various corrosion problems during the hydrogenation reaction. In addition, productivity is poor due to low yield.

On the other hand, the petroleum resin can be used as it is after the polymerization. Recently, the petroleum resin is used in the form of a hydrogenated petroleum resin produced by further performing a hydrogenation process to improve physical properties.

Hydrogenated petroleum resin is a thermoplastic resin produced from a petroleum chemical plant using high unsaturated hydrocarbon as a raw material in high-temperature pyrolysis fluid such as naphtha, and is excellent in safety against heat and ultraviolet rays (UV) Medical supplies, woodworking supplies, and sanitary goods.

In the case of a hydrogenated petroleum resin, it is difficult to completely remove unreacted raw materials, solvents and low molecular weight oligomers during the production process. Therefore, in the course of manufacturing hygiene products such as diapers sprayed with a high temperature adhesive, It can also occur when the odor triggers the odor and the final product is unpacked. In addition, the hydrogenated petroleum resin has a unique unpleasant odor upon melting at a high temperature, thereby adversely affecting the working environment. In addition, when applied to a hygiene product, the needs of consumers who need sensitive and sensitive skin due to odor inducing factors There was a limit to satisfaction.

Therefore, as the living standards of consumers increase, the demand for petroleum resin used in hygiene products is increasing day by day, so it is urgently required to develop a technique for improving the odor of petroleum resin.

Accordingly, US Patent No. 5,652,308 discloses a tackifying resin in which propylene as a C3-based monomer and DCPD produced from a C5-based monomer are copolymerized using a metallocene catalyst to partially replace a C5-based monomer with a C3-based monomer There is one. However, when the petroleum resin is produced by the above method, expensive metallocene catalysts which are very vulnerable to oxygen and moisture must be used. Therefore, the process design is complicated, the production cost is high and the yield is also less than 30% There is a problem that it is difficult to actually put it into practical use.

U.S. Patent No. 5,410,004 (Apr. 25, 1995), Thermal polymerization of dicyclopentadiene U.S. Patent No. 5,652,308 (July 27, 1997), Tackifiers and a process to obtain tackifiers

In order to solve the above problems, Applicants have conducted various studies and have found that hydrogenated petroleum resin is produced by performing a thermal polymerization process instead of a complicated catalytic polymerization process, thereby producing a hydrogenated petroleum resin, It was found that when the olefin-based monomer is used together, the final hydrogenated petroleum resin obtained has improved adhesion and heat resistance, improved odor, and improved properties when applied to an adhesive.

Accordingly, it is an object of the present invention to provide a method for producing a hydrogenated petroleum resin which can be practically used in a simplified process.

Another object of the present invention is to provide a hydrogenated petroleum resin which is produced by the above-mentioned method and has improved physical properties and improved odor.

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

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

(Wherein R ₁ is H or a methyl group, R ₂ is a C ₁ to C 18 alkyl group, 0? M? 10, and 0? N? 10)

The present invention also relates to a process for producing a petroleum resin, comprising the steps of: preparing a petroleum resin by thermally polymerizing dicyclopentadiene and a C3 to C20 olefin monomer; And

And performing a hydrogenation reaction of the petroleum resin with a hydrogenation catalyst. The present invention also provides a process for producing a hydrogenated petroleum resin.

Further, the present invention provides the use of the hydrogenated petroleum resin in an adhesive composition.

The method of producing a hydrogenated petroleum resin according to the present invention can solve the supply and demand problem of raw materials by replacing the C3-based olefin which has been used as a raw material of the conventional petroleum resin with an olefin having 6 to 20 carbon atoms, By using the polymerization process, the polymerization yield can be greatly improved.

In particular, the hydrogenated petroleum resin produced by the production method of the present invention solves the problem that unpleasant odor peculiar to the conventional petroleum resin can not be improved, and the odor is hardly generated.

In addition, the hydrogenated petroleum resin produced by the above production method is excellent in odor, excellent in adhesion performance, has a high softening point, is transparent, has a low molecular weight, is excellent in color, and has good compatibility with natural rubber, It can be used effectively as an adhesive in various fields, and it can enhance the competitiveness especially when it is applied to sanitary articles.

Fig. 1 is a schematic diagram for explaining the NMR spectrum analysis proposed in the present invention, in which (a) shows the peak area and (b) shows the full width at half maximum.
Fig. 2 is a flow chart showing a method for producing a hydrogenated petroleum resin as 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 a 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 a 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 a petroleum resin before hydrogenation of Comparative Example 1 according to the present invention.
11 is a ¹ H-NMR spectrum of petroleum resin after hydrogenation of Comparative Example 1 according to the present invention.

The present invention provides a petroleum resin having a novel structure which is improved in odor and can be applied to an adhesive or a pressure sensitive adhesive.

Hydrogenation Petroleum resin

The hydrogenated petroleum resin according to the present invention is prepared by the thermal polymerization of dicyclopentadiene and an olefin monomer followed by a hydrogenation reaction and includes a repeating unit represented by the following general formulas (1) and (2)

 [Chemical Formula 1]

(2)

(Wherein R ₁ is H or a methyl group, R ₂ is a C ₁ to C 18 alkyl group, 0? M? 10, and 0? N? 10)

Preferably, R < ₁ > is H and 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. 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. Of these, a butyl group which is C4 or higher alkyl group, a pentyl group , A hexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, or a tetradecyl group is preferable.

The hydrogenated petroleum resin according to the present invention contains a repeating unit represented by the above general formulas (1) and (2), but is saturated in the absence of a double bond in the molecular structure, and these repeating units have a copolymerized form.

In this case, the shape of the copolymer is expressed as described above for the sake of convenience, but it is not particularly limited in the present invention, and examples thereof include random copolymers, alternative copolymers, block copolymers, graft copolymers, copolymers and starblock copolymers.

Specifically, the repeating unit represented by the formula (1) is a repeating unit derived from a dicyclopentadiene, and the repeating unit represented by the formula (2) is a repeating unit derived from a polymerization reaction of a dicyclopentadiene and an olefin monomer as a comonomer. . ≪ / RTI > The odor of the petroleum resin is improved through the use of the olefin-derived alkyl group constituting the repeating unit of the above formula (2). At this time, the content of the alkyl group derived from the olefin in the petroleum resin may be 10 to 50 mol%, preferably 10 to 45 mol% in the whole petroleum resin. If the content of the alkyl group is less than the above range, it may be difficult to exhibit an improvement in adhesiveness and an improvement in odor due to copolymerization with an olefin-based monomer. On the other hand,

The repeating units of the formulas (1) and (2) are preferably present in a predetermined molar ratio, and are specifically present in a proportion of 40 to 90 mol% of the repeating unit represented by the formula (1) and 10 to 60 mol% of the repeating unit represented by the formula (2). If the number of repeating units represented by the general formula (2) is relatively small, improvement effects such as odor and adhesion performance can not be secured. On the other hand, if the repeating units are excessively used, the physical properties of the petroleum resin itself are lowered.

Structural analysis of the hydrogenated petroleum resin according to the present invention having the above-described structure can be performed through a nuclear magnetic resonance (NMR) spectrometer ( ¹ H-NMR). Through the peak analysis, Can be specified.

¹ H-NMR analysis is an analytical method for determining the atom to which a hydrogen atom is bonded in a compound, and in which functional group it is contained and the spatial arrangement. This method is used for identification and identification of compounds, and can be used for quantitative analysis of a mixture and estimation of molecular structure as well as for measurement of binding state change.

^{In the 1} H-NMR spectrum, the proton (H ⁺ ) in the same relationship in the molecule appears as one peak, and if it is closely related to another nucleus, it divides into multiple lines. At this time, the position of the chemical shift (that is, the interval of frequency, ppm) differs depending on the proton present in the single bond and the double bond (i.e., unsaturated bond), and the intensity is also different. That is, the chemical shift data can be used to extract information on the presence of a certain type of proton in the molecule, the ratio of each proton through the integral, and which protons are adjacent to each other through coupling.

The hydrogenated petroleum resin represented by the present invention has a repeating structure of the above formulas (1) and (2), wherein the repeating unit of formula (1) consists of a cyclic structure derived from dicyclopentadiene, Lt; RTI ID = 0.0 > linear < / RTI > As a result, it is possible to identify the hydrogenated petroleum resin by confirming the peak specified by R ₂ in the general formula (2).

The ¹ H-NMR spectrum of the hydrogenated petroleum resin does not appear as a peak like a compound, and due to the presence of a large number of protons, they affect each other, and peaks are present in a predetermined area as shown in FIGS. Generally, the greater the number of protons (hydrogen), the more the R ₂ may be long, or the R ₂ -substituted repeat unit of formula (2) may have a large content. Therefore, in the present invention, the petroleum resin is specified by considering both of the two 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 related to the repeating units of the formulas (1) and (2) have a large number of peaks up to 7.5 ppm. Among them, the peak of 0.8 to 1.4 ppm is the proton peak derived from R ₂ , and the other is the proton peak derived from the ring structure of dicyclopentadiene.

The peak of 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 a parameter and a case where a peak width is a parameter. That is, quantitative analysis and qualitative analysis are possible by analyzing the parameters related to the peak area and the peak width, and can be specified through the hydrogenated petroleum resin disclosed in the present invention.

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

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

In addition, the width of a 'ppm peak shown in the present invention of FIG. 1 (b) is a peak at full width at half maximum (FWHM), which is a peak including a baseline at a' Means a width at 1/2 point (H / 2) of the height (H).

(i) NMR peak area parameter

The hydrogenated petroleum resin of the present invention can be defined as a parameter of the peak area, wherein the peak area follows the definition as shown in Fig. 1 (a).

The alkyl group of R < ₂ > The peak appears in the range of 0.8 to 1.4 ppm, and the peak is divided into two bifurcations in this range. Wherein the peak at 0.8-1.0 ppm and the peak at 1.0-1.4 ppm are related to the content of R ₂ to some extent and the ratio between the peak at 0.8-1.0 ppm and the peak at 1.0-1.4 ppm is R ₂ Is the peak at which the length of the carbon number of the olefin is known, that is, the type of the olefin used.

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

Preferably, the hydrogenated petroleum resin of the present invention has a peak area of 0.8 to 1.0 ppm relative to a peak area of 1.4 to 7.5 ppm in the NMR spectrum obtained after ¹ H-NMR measurement of 0.2 or more, preferably 0.2 to 0.8, more preferably And has a range of 0.5 to 0.7 as follows. The area ratio is related to the content of R ₂ and is related to the effect to be obtained by substitution of the alkyl group. That is, if the area ratio is out of the above range, the effect of improving the heat resistance and improving the odor of the petroleum resin can not be secured.

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 of 0.5 or more, preferably 0.5 to 0.8, 0.6 to 0.7. The above-mentioned area ratio relates to the kind of R < ₂ > and relates to an effect to be obtained by substitution of an alkyl group. That is, if the area ratio is out of the above range, the effect of improving the heat resistance and improving the odor of the petroleum resin can not be secured.

The alkyl group (R ₂ ) in the hydrogenated petroleum resin is present to a certain extent through the NMR peak area parameter in the specific range, and the kind of the olefin monomer used can be predicted. At this time, any one or more of the area ratios of the respective peaks may be satisfied, and more preferably all of them can be satisfied.

(ii) NMR peak width parameter

The hydrogenated petroleum resin of the present invention can be defined as a parameter of the full width at half maximum (FWHM) of the peak, wherein the peak area follows the definition shown in FIG. 1 (b).

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 to the full-width full width parameter.

Preferably, with respect to the substitution degree of R ₂ , the full width at half maximum at 0.85 ppm was confirmed, and the full width at half maximum at 1.20 ppm was confirmed with respect to the carbon number of R _{2. As} a result, the half width at 0.85 ppm peak was 0.1 ppm or less And the full width at half maximum of the 1.20 ppm peak is preferably 0.4 ppm or less, more preferably 0.01 to 0.4 ppm.

As described in (i) above, the half-width full-width parameter is a limited range capable of achieving improvement in adhesion performance and improvement in solubility through the use of an olefin-based 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, and more preferably all of them can be satisfied.

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 캜, and a color (APHA color) of 1 to 100. If the weight average molecular weight is less than 500 g / mol, the adhesive strength may be lowered. If the weight average molecular weight is more than 3000 g / mol, the compatibility may be insufficient. If the softening point is lower than 90 ° C, the adhesive strength may be lowered. If the softening point is higher than 150 ° C, it is not preferable from the viewpoint of difficult application in the manufacturing process.

The weight-average molecular weight is related to the application field of the hydrogenated petroleum resin. For example, the weight-average molecular weight is a range that can sufficiently exert its functions when applied to the adhesive field proposed in the following applications. When the molecular weight is less than the above range, the adhesive ability is lowered. On the other hand, the molecular weight exceeds the range and compatibility with other resins may be lowered.

The softening point refers to the temperature at which the softening point is deformed by heat to cause softening. When the softening point is too low when applied to the adhesive field, the petroleum resin itself may melt during storage of the petroleum resin. On the other hand, The adhesive property of the adhesive may be deteriorated.

In addition, the APHA color related to color is applied to measure the chromaticity of a clear liquid and solid state, and is usually expressed by dividing the color into 1 to 500 stages, which is correlated with the yellowness index . The hydrogenated petroleum resin of the present invention has an APHA value of 1 to 100, and when it is more than 100, it shows opaque characteristics or when mixed with other resins, the color becomes turbid and its value as a product is lowered.

In the present experimental example, the polyolefin rubber and the wax were mixed at a predetermined ratio, and the mixture was heated until it became transparent. After cooling, the temperature at which the resin composition was blurred The compatibility was measured as a cloud point. That is, the compatibility means that the hydrogenated petroleum resin of the present invention and other resins can be mixed well at room temperature to 150 ° C.

Hydrogenation Petroleum resin  Manufacturing method

The hydrogenated petroleum resin according to the present invention comprises the steps of: preparing a petroleum resin through thermal polymerization of dicyclopentadiene and an olefin which is a C3 to C20; And

And then hydrogenating the petroleum resin with a hydrogenation catalyst to produce a hydrogenated petroleum resin.

Each step will be described in detail below.

(S1) Thermal polymerization  Reaction step

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

The olefinic monomer used as the comonomer is an olefinic compound up to C20, including C3-based olefins, which have been used as main materials of conventional petroleum resins. Preferably, the olefin-based monomer may be a linear or branched alpha-olefin-based monomer.

The above-mentioned alpha-olefin-based monomer is more flexible than branched alpha-olefin and superior in fluidity and structural penetration when linear alpha-olefin is used, thus securing high wettability to a substrate when used as an adhesive or a pressure- have. At this time, the alpha-olefin monomer may be one kind of the above-mentioned monomers or a mixture of two or more kinds, and is not particularly limited in the present invention.

Examples of olefinic monomers that can be used include ethylene (or ethene), propylene (or propene), 1-butene, 1-pentene, 1-hexene, Linear alpha-olefins such as dodecene, 1-tetradecene, 1-hexadecene and 1-aidocene, isobutylene, 3-methyl-1-butene, Butene, 4-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl- Branched aliphatic olefins, branched aliphatic olefins, branched aliphatic olefins, branched aliphatic olefins, and mixtures thereof. More preferably, linear alpha olefins are used, and most preferably 1-hexene, 1-heptene, , 1-decene, dodecene, and the like.

For example, Scheme 1 shows the reaction of dicyclopentadiene with 1-hexene, which is a C6 olefin.

[Reaction Scheme 1]

In particular, in the present invention, the polymerization of the dicyclopentadiene and the olefin monomer is carried out through thermal polymerization, not catalytic polymerization.

When a certain level of heat is applied to the dicyclopentadiene and the olefin-based monomer, the radicals themselves form an initiating reaction, and the petroleum resin is produced through the continuous polymerization reaction. Such thermal polymerization does not use an initiator, so that it is possible to solve problems of increase in cost and purity of petroleum resin due to use of the initiator.

The molar ratio of the reaction material in the thermal polymerization of the dicyclopentadiene and the olefin monomer is used in a molar ratio of dicyclopentadiene to olefin monomer in the range of 1: 0.2 to 1: 0.5, preferably 1: 0.25 to 1: 0.45 . The molar ratio is related to the physical properties of the finally obtained hydrogenated petroleum resin. If it is less than the above range, it is difficult to produce a hydrogenated petroleum resin having a desired level of physical properties by using too little of an olefin monomer. On the other hand, The content of the cyclopentadiene is relatively reduced, and the physical properties of the hydrogenated petroleum resin finally produced are lowered, so that it is appropriately controlled within the above range.

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

When a solvent is used for the solution polymerization and this step is carried out by solution polymerization, the dicyclopentadiene solution is prepared by dissolving the dicyclopentadiene in a solvent, adding the olefinic monomer to the obtained dicyclopentadiene solution Post thermal polymerization is performed.

The solvent may be any solvent as long as it can sufficiently dissolve the above-mentioned dicyclopentadiene, and is not limited to the present invention. Examples of the solvent include toluene, methylene chloride, hexane, xylene, trichlorobenzene, alkylbenzene, acetonitrile, dimethylformamide, N-methylpyrrolidone, dimethylacetamide, dimethylsulfoxide, gamma-butyrolactone, , Acetone, and a mixed solvent thereof.

The content of the solvent can be any level as long as it can sufficiently dissolve the dicyclopentadiene. For example, it is used in the range of 2 to 10 moles per mole of dicyclopentadiene.

The thermal polymerization is carried out at a temperature at which the initiation and polymerization of the dicyclopentadiene and the olefin monomer can sufficiently take place, and the temperature can be changed depending on the kind of the dicyclopentadiene and the olefin monomer.

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

The temperature is directly related to initiation and polymerization reaction, and initiation does not occur at temperatures below this range. On the other hand, at temperatures above the above range, decomposition of the dicyclopentadiene or olefin monomer as a raw material or gel formation And the polymerization rate control is not easy.

In addition, the reaction time is related to the yield. If the reaction time is less than the above-mentioned range, the yield may be low. On the contrary, if the reaction is carried out for a long time, there is no large increase in the yield.

In particular, by thermally polymerizing dicyclopentadiene and an olefin-based monomer, it is possible to solve the problem of difficulty in supplying and supplying raw materials of C5 olefin, which has been used as a main raw material in conventional petroleum resins, Can be solved. In addition, when the petroleum resin is produced by the thermal polymerization in this way, the catalyst removal step which was an essential step in the cationic catalyst method, which is a conventional petroleum resin production method, may not be required, and the yield can be remarkably improved to 90% or more desirable.

(S2) Hydrogenation step

Next, the hydrogenated petroleum resin is prepared by adding a hydrogenation catalyst to the petroleum resin prepared above and performing a hydrogenation reaction.

The hydrogenation reaction is a reaction in which hydrogen is added to an unsaturated double bond to form a single bond, and a hydrogenated petroleum resin in which a double bond is completely eliminated through hydrogenation of a petroleum resin is produced.

For example, Scheme 2 below shows the steps of preparing a hydrogenated petroleum resin made from dicyclopentadiene and 1-hexene, which is a C6 olefin.

[Reaction Scheme 2]

The hydrogenation reaction proceeds by the addition of the hydrogenation catalyst and involves a high temperature process, so that the temperature control requirement is severe and high pressure must be maintained. Preferably, the hydrogenation reaction is carried out at 150 to 300 DEG C under a pressure of 50 to 150 bar. If the temperature and pressure are less than the above range, the hydrogenation reaction can not be sufficiently carried out. On the contrary, if the temperature and pressure exceed the above range, the molecular structure may be destroyed by severe reaction conditions.

The hydrogenation catalyst to be used at this time is not particularly limited in the present invention, and 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, Pd is used.

The hydrogenation catalyst is used in a molar ratio of 0.001 to 0.5, preferably 0.05 to 0.2, based on 1 mole of dicyclopentadiene. If it is used in an amount of less than 0.001 mol based on 1 mol of dicyclopentadiene, the reactivity may be insufficient, and when it exceeds 0.5 mol, the use of a large amount of catalyst is not economical.

The process for producing a hydrogenated petroleum resin according to the present invention can be produced from a hydrogenated petroleum resin with high yield through thermal polymerization and can simplify the process, reduce the cost, and can be easily applied to the practical process.

Specifically, there is no need to use an expensive catalyst used in the conventional catalytic polymerization, and the catalyst removal process is fundamentally eliminated after the completion of the reaction, thereby simplifying the process itself and reducing the device cost and process cost. .

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

Usage

The petroleum resin produced in the present invention can impart point and adhesive properties to hot melt adhesives, pressure sensitive adhesives, inks, paints and road marking paints, and can be blended with various resins such as natural rubber and synthetic rubber, Can be usefully used.

The present invention also relates to a petroleum resin comprising a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (2); Styrenic block copolymers such as styrene-butadiene block copolymers, styrene-isoprene block copolymers, styrene-isoprene-styrene block copolymers, styrene-butadiene block copolymers and styrene-butadiene-styrene block copolymers, polyethylene, Polymers selected from ethylene based polyolefin block copolymers such as ethylene vinyl acetate and propylene-ethylene copolymers; And an oil component selected from the group consisting of synthetic waxes such as paraffin wax and microstalin wax, animal wax, vegetable natural wax, aromatic oil, naphthenic oil and paraffin oil.

 The adhesive prepared from the adhesive composition has a softening point of 50 to 150 캜, a melt viscosity of 300 cps to 10,000 cps at 160 캜, and a viscosity of 200 cps to 8,000 cps at 180 캜.

If the softening point of the adhesive is less than 50 캜, the adhesive strength may be deteriorated. If the softening point is more than 150 캜, it is not preferable in view of difficulty in application to the manufacturing process.

If the melt viscosity is higher than 10,000 cps at 160 캜, the workability may deteriorate. If the viscosity is less than 300 cps, the adhesive strength may decrease. If the melt viscosity is higher than 8,000 cps at 180 캜, the workability may deteriorate.

The adhesive made of the adhesive composition may be used as a hot melt adhesive (HMA) or a hot melt sensitive adhesive (HMPSA).

In the case of hot melt type adhesives, compatibility is less than 100 ° C, hardness is 30 to less than 90 ° C, open time is more than 5 seconds to less than 30 seconds, set time is more than 0.1 second to less than 5 seconds, .

In the case of the pressure-sensitive adhesives, it is less than 40 cm at the initial stage and less than 40 cm at the initial stage in the ball tack method, at least 500 gf / in at the initial peel strength and at least 500 gf / min, and more than 30 min after aging. The SAFT method showed an initial temperature of 40 ° C or higher and a temperature of 40 ° C or higher after aging, indicating excellent properties as a pressure-sensitive adhesive.

As described above, the adhesive according to the present invention is produced by the hydrogenated petroleum resin having no double bond due to the hydrogenation reaction and being produced by thermal polymerization, so that unreacted starting material, solvent and low molecular weight oligomer are not generated, An unpleasant smell (odor) is improved. Such adhesives can be suitably used in hot melt adhesive or adhesive for sanitary articles in contact with human bodies such as diapers, sanitary napkins, adult diapers and the like in all fields requiring the use of adhesives

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

[Example]

Example  One

A 1 L autoclave was charged with 1.5 mol of dicyclopentadiene (DCPD) dissolved in 4 mol of toluene as a solvent, 0.5 mol of 1-hexene was added thereto, and the reactor was maintained at a temperature of 270 ° C And the reaction was terminated. After completion of the reaction, the resulting petroleum resin was distilled at 240 DEG C for 5 minutes to recover unreacted oil fractions, and 55 g of the remaining petroleum resin was obtained. To 55 g of the obtained petroleum resin was added toluene 1.5 times as a hydrogenation solvent to completely dissolve it, and a 1 L autoclave was charged.

Then, 0.2 mol of a palladium catalyst was added thereto, and after the reactor was tightened, the hydrogenation reaction was carried out at a hydrogen pressure of 80 bar and a temperature of 230 캜 for 90 minutes. After the reaction was completed, the reaction product liquid was distilled at 260 DEG C for 10 minutes under a vacuum of 10 torr to prepare 50 g of a hydrogenated petroleum resin. Each of the detailed components was prepared in the contents shown in Table 1.

Whether or not the petroleum resin before hydrogenation and the petroleum resin after hydrogenation had been polymerized was confirmed by measurement using a nuclear magnetic resonance spectrometer (Bruke 500 NMR, 14.1 telsa). The results are shown in FIGS. 3 and 4 . That is, the ¹ H-NMR spectrum of the petroleum resin before the addition of hydrogen was confirmed. As shown in FIG. 3, a peak indicating a methyl group (-CH ₃ ) derived from 1-hexene between 0.85 and 0.95 ppm in ¹ H- (Peak) increases. 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.

The results of ¹ H-NMR spectroscopy confirming the structure of the petroleum resin after the hydrogenation showed that the peaks indicating the methyl group (-CH ₃ ) of 1-hexene between 0.85 and 0.95 ppm during ¹ H-NMR measurement Peak is increased and the peak indicating the <-CH ₂ -> chain of 1-hexene is increased between 1.20 and 1.30 ppm at the same time, it can be seen that DCPD and 1-hexene are copolymerized resins, and at the same time, 4.9 to 6.5 ppm It is found that the hydrogen addition is completely performed.

At this time, in the ¹ H-NMR spectrum measurement method, the peak between 0.85 and 0.95 ppm is the olefin methyl group, the peak between 1.20 and 1.30 ppm is the peak of the <-CH ₂ -> chain of the olefin and between 4.9 and 6.5 ppm The peak is a peak of the double bond of the dicyclopentadiene. By comparing the values of the respective peaks, as shown in the results of FIGS. 3 and 4, it is possible to determine whether the DCPD and the olefin (olefin) Can be confirmed.

Example  2-14

The petroleum resins of Examples 2 to 14 were produced by the method of Example 1, according to the conditions described in Table 1 below.

The results of ¹ H-NMR spectroscopy of the petroleum resin before hydrogenation and the petroleum resin after hydrogenation prepared in Example 5 were shown in FIG. 5 (before hydrogenation) and FIG. 6 (after hydrogenation) 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 The results of ¹ H-NMR spectroscopy of all petroleum resins are shown in FIG.

Comparative Example  One

In a 1 L autoclave, 2.0 mol of dicyclopentadiene (DCPD) was dissolved in 4 mol of toluene as a solvent, and the reaction was terminated after maintaining the reaction temperature at 270 DEG C for 2 hours. After completion of the reaction, the resulting petroleum resin was distilled at 240 DEG C for 5 minutes to recover unreacted oil fractions, and 57 g of the remaining petroleum resin was obtained.

To 57 g of the obtained petroleum resin was added toluene 1.5 times as a hydrogenation solvent, completely dissolved, and a 1 L autoclave was charged. After 0.2 mol of a palladium catalyst was added thereto and the reactor was tightened, hydrogenation was carried out at a hydrogen pressure of 80 bar and a temperature of 230 캜 for 90 minutes. After the completion of the reaction, the reaction product liquid was distilled at 260 DEG C for 10 minutes under a vacuum of 10 torr to prepare 53 g of a hydrogenated petroleum resin. Each of the detailed components was prepared in the contents shown in Table 1.

Whether or not the petroleum resin before hydrogenation and the petroleum resin after hydrogenation had been polymerized was confirmed by measurement using a nuclear magnetic resonance spectrometer (Bruke 500 NMR, 14.1 telsa), and the results are shown in Figs. 10 and 11 Respectively.

Comparative Example  2, 3

The petroleum resins of Comparative Examples 2 and 3 were produced by the method of Comparative Example 1, under the conditions described in Table 1 below.

Comparative Example  4, 5: catalytic polymerization

In a 1 L autoclave, dicyclopentadiene (DCPD) was dissolved in 500 ml of toluene as a solvent, and tricyclodecene (TCDE), a polymerization regulator, was added. The initiator was added thereto, and after the reactor was tightened, the olefin was added, and the reaction was carried out by adding the catalyst to the mixture. 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 DEG C for 5 minutes to recover unreacted oil fractions to obtain the remaining petroleum resin.

To 300 g of the obtained petroleum resin was added toluene 1.5 times as a hydrogenation solvent to completely dissolve it, and a 1 L autoclave was charged. 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 tightening. After the completion of the reaction, the reaction product liquid was distilled at 250 DEG C for 5 minutes under a vacuum of 5 torr to prepare a hydrogenated petroleum resin. Each of the detailed components was prepared in the contents shown in Table 1.

division

Raw material (mol) The catalyst (mol) Initiator (mol) Hydrogenation
catalyst
(mol) Polymerization conditions Hydrogenation condition DCPD Olefin AlCl ₃ t-BuCl Pd Temperature
(° C) time
(hr) Temperature
(° C) time
(hr) Propylene Butene Piperylene 1-hexene 1-octene 1-decene 1-dodecene 2-octene Example 1 1.5 0.5 0.2 270 2 230 1.5 Example 2 1.5 0.5 0.2 280 2 230 1.5 Example 3 1.7 0.3 0.2 280 2 230 1.5 Example 4 1.5 0.5 0.2 270 2 230 1.5 Example 5 1.5 0.5 0.2 280 2 230 1.5 Example 6 1.7 0.3 0.2 280 2 230 1.5 Example 7 1.5 0.5 0.2 280 2 230 1.5 Example 8 1.5 0.5 0.2 280 2 230 1.5 Example 9 1.4 0.6 0.2 280 2 230 1.5 Example 10 1.0 1.0 0.2 280 2 230 1.5 Example 11 1.0 1.0 0.2 280 2 230 1.5 Example 12 1.5 0.5 0.2 270 2 230 1.5 Example 13 1.5 0.5 0.2 280 2 230 1.5 Example 14 1.5 0.5 0.2 290 2 230 1.5 Comparative Example 1 2.0 0.2 270 2 230 1.5 Comparative Example 2 2.0 0.2 280 2 230 1.5 Comparative Example 3 2.0 0.2 290 2 230 1.5 Comparative Example 4 0.8 1.6 0.038 0.075 0.2 40 2 230 1.5 Comparative Example 5 0.8 1.6 0.038 0.075 0.2 40 2 230 1.5

[ Experimental Example ]

< Experimental Example  1: Evaluation method of resin properties>

1) Yield

The yield was obtained by the following formula.

Yield (%) = resin obtained (g) / monomer added (g) * 100

(2) Softening point

The softening point was measured using the ring and ball softening method (ASTM E 28). The resin was melted into a ring-shaped mold, and the resin was placed in a beaker containing glycerin. The ball was placed in a ring containing the resin, and the temperature was raised by 2.5 ° C per minute to melt the resin (softening point) The results are shown in Table 3.

(3) Molecular weight

The polystyrene reduced weight average molecular weight and the number average molecular weight were measured by gel permeation chromatography (GPC) (PL GPC-220). The hydrogenated petroleum resin to be measured was dissolved in 1,2,4-trichlorobenzene so as to have a concentration of 0.34 wt%, and 288 μL was injected into GPC. The mobile phase of GPC was loaded with 1, 2, 4-trichlorobenzene at a flow rate of 1 mL / min and analysis was performed at 130 ° C. The column was connected in series with two Guard columns and one PL 5μ mixed-D. The detector was measured as the temperature is raised to 250 ℃ to 10 ℃ / min using a differential scanning calorimeter, the process proceeds to analysis under N ₂ atmosphere are shown in Table 3. The analysis to 2nd scan.

Mw in the following Table 3 means weight average molecular weight, and MWD means Mw / Mn.

(4) Hydrogenation Petroleum resin  Analysis of the content of olefins in

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

(5) Color ( APHA )

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

(6) Specific gravity

Specific gravity was measured by ASTM D71. Specifically, 5 g of the hydrogenated petroleum resin was dissolved in a hotplate at 200 ° C, poured into a spherical ring, and the hydrogenated petroleum resin hardened in a spherical shape was taken out of the ring and put in a QUALITEST (Densimeter SD-200L) Respectively.

(7) Odor intensity

The petroleum resin was assessed on the strength of odor by five persons. 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 the hot state and evaluate the odor generated from the petroleum resin. The odor intensity was calculated by dividing the odor intensity into numerical values on the classification table in Table 2 and then giving a score from 0 to 5.

Degree Odor sensitivity Explanation 0 Odorless A state in which no odor is detected due to relative odor One Detection smell The state of being able to sense the smell but not the smell 2 Normal odor A state of being able to know what the smell is 3 Strong odor Easily detectable strong odor
(The condition of taking a unique smell of the crozone in the hospital) 4 Extreme odor A very strong smell
(In a conventional toilet I was in a severe condition 5 Unbearable odor It is a strong smell that is hard to bear,

&Lt; Evaluation results of resin characteristics >

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

division yield
(%) Softening point
(° C) Molecular Weight The olefin content (mol%) in the hydrogenated petroleum resin color
APHA importance Odor intensity
Mw MWD
Example 1 91 85 850 1.8 21 20 1.05 1.0 Example 2 100 100 1000 2 23 20 1.05 1.0 Example 3 100 110 1150 2.1 13 30 1.05 0.9 Example 4 90 88 870 1.7 20 20 1.05 0.9 Example 5 99 102 1100 2 21 20 1.05 0.8 Example 6 100 115 1210 2 12 30 1.05 0.7 Example 7 100 105 1300 2 19 30 1.05 0.5 Example 8 100 109 1320 2 17 35 1.05 0.5 Example 9 90 100 1150 1.8 15 30 1.05 0.6 Example 10 60 75 800 2.2 35 20 1.1 2.5 Example 11 75 83 820 2.1 41 20 1.08 2.0 Example 12 80 80 705 1.9 19 20 1.08 2.0 Example 13 85 86 810 2.1 21 20 1.08 2.0 Example 14 95 101 1050 2.2 22 20 1.1 2.2 Comparative Example 1 90 100 550 1.7 0 15 1.1 3.5 Comparative Example 2 99 120 670 1.9 0 20 1.1 3.5 Comparative Example 3 100 160 700 2.2 0 25 1.1 3.9 Comparative Example 4 50 95 1390 2.4 35 30 1.05 1.2 Comparative Example 5 52 97 1750 2.7 33 30 1.05 1.0

As shown in Table 3, it can be confirmed that Examples 1 to 9 were produced with a yield of 90% or more. It can also be seen that the compositions of all the Examples were significantly improved when compared to the compositions of the Comparative Examples. Among them, as in Examples 1 to 12, it can be seen that excellent results are obtained when C4 or more alkyl groups are substituted.

In addition, in Comparative Examples 4 and 5, it was found that the polymerization was carried out through a cation catalyst, and the yield was remarkably decreased, and the molecular weight and the molecular weight distribution were considerably high.

Therefore, the process for producing the petroleum resin according to the present invention is different from the process of hydrogenation in the presence of a cationic catalyst, which is a conventional method for producing petroleum resin, through low temperature polymerization at about 40 ° C, The polymerization is carried out through the polymerization and the hydrogenation reaction is carried out. Thereby, a separate catalyst removal step is not necessary, and the yield is increased by this, so that the productivity is remarkably increased and the level of odor is almost equal or even higher.

The results of ¹ H-NMR spectroscopy of Examples 1 and 5 and Comparative Example 1 are shown in Table 4.

A1: Peak area of 0.8 to 1.0 ppm in &lt; ¹ &gt; H-NMR spectrum

A2: Peak area of 1.0 to 1.4 ppm in &lt; ¹ &gt; H-NMR spectrum

A3: Peak area of 1.4 to 7.5 ppm in &lt; ¹ &gt; H-NMR spectrum

Hydrogenated petroleum resin raw material Area ratio parameter Full-width full width parameter drawing
A1 / A3 A2 / A3 0.85 ppm 1.20 ppm Comparative Example 1 DCPD 0.24 0.43 > 1.8 > 0.1 11 Example 1 Hex / DCPD 0.27 0.65 0.08 0.2 4 Example 5 Oct / DCPD 0.26 0.74 0.0523 0.1188 6

< Experimental Example  2: Preparation of adhesive and measurement of physical properties>

In order to confirm the performance of the hydrogenated petroleum resin prepared in the present invention as an adhesive, the following procedure was performed.

&Lt; Evaluation method of adhesive performance >

The compatibility, viscosity and softening point were determined by the method used in the evaluation of resin properties.

(1) Hardness (A)

124ASTM standard Shore A hardness meter. The sample to be measured was laid on a flat surface and the sample was pierced with a sharp point of the hardness meter to record the measured value.

(2) Open time

Open time was measured by JIT hot melt tester. After applying a certain amount of adhesive to the corrugated board of 5 cm in width and 5 cm in length, the corrugated cardboard was stretched from 0 to 5 seconds after 5 cm by 10 cm by 10 cm. When the graph was drawn, the time to start descending suddenly was recorded.

(3) Set time

Set time was measured with a hot melt tester from JIT Corporation. After applying a certain amount of adhesive to the corrugated board of 5 cm in width and 5 cm in length, the corrugated cardboard was stretched from 0 to 0.5 cm by 5 cm by 10 cm. The time at which the value of the Y-axis force starts to become constant when the graph is drawn is recorded.

(4) Peel strength

UTM equipment. First, a sample (adhesive) was applied to the PET film to a thickness of 25 micrometers to prepare a tape. This was attached to a SUS-304 steel plate. The PET film was attached to the UTM grip and measured at a speed of 30 mm / min. At this time, the numerical value inputted to the UTM equipment means the adhesive force (kgf / in).

(5) Adhesion evaluation: Ball Tack

Adhesion was evaluated by the ASTM D3121 method.

The tape of the test specimen, which was coated with an adhesive of 20 to 30 micrometers, was cut into a length of 10 cm and a length of 50 cm. A 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 distance between the rolls was measured by rolling a steel ball No. 9 thereon. The less the ball rolls, the better the performance of the Tack.

(6) Evaluation of adhesion: Holding power

The adhesive strength was evaluated by the ASTM D3330 method.

Adhesive tapes of 20 to 30 micrometer specimens were cut by 2 inches by 6 inches. The specimens were placed on a release paper and made to a width of 1 inch and a length of 2 inches, and then they were attached to a cleaned SUS 304 steel plate (the unattached test specimen was attached so as to be about 2 cm or more, The roll was once reciprocated and squeezed). The test specimens not attached to the SUS 304 steel plate were cut with scissors to a length of about 2 cm. A specimen not attached to the SUS 304 steel plate was inserted into the cohesion measuring ring and adhered to the passing test specimen. Two screws were attached in parallel on the front and back sides of the SUS 304 steel plate with the test piece fixed with a fixing scotch tape, and two screws were stuck between the coil for measuring the cohesion and the SUS304 steel plate in parallel. The remaining test specimens were cut so that the test specimen was 1 inch wide and 1 inch high on the SUS 304 steel plate.

Shear was placed on the SUS steel plate holder in the test oven. 1 kg weight was attached to the holding power measuring ring attached to the specimen. The timer recorded an additional time of fall.

(7) Evaluation of adhesion strength: SAFT

The adhesive strength was evaluated by the ASTM D3654 method.

Test specimen tapes with adhesive applied at 20 to 30 microns were cut by 2 inches * 6 inches. The specimens were placed on a release paper and made to a width of 1 inch and a length of 2 inches, and then they were attached to a cleaned SUS 304 steel plate (the unattached test specimen was attached so as to be about 2 cm or more, The roll was once reciprocated and squeezed). The test specimens not attached to the SUS 304 steel plate were cut with scissors so as to be about 2 cm. A specimen not attached to the SUS 304 steel plate was inserted into the cohesion measuring ring and adhered to the passing test specimen. Two test pieces were stuck to each other in parallel on the horizontal end portion of the SUS 304 steel sheet with the test piece adhered thereon. Two staples were stuck between the cohesion measuring ring and the SUS304 steel plate to fix them in parallel. The remaining test specimens were cut so that the test specimen was 1 inch wide and 1 inch high on the SUS 304 steel plate.

 Shear was placed on the SUS steel plate holder in the test oven. 1 kg weight was attached to the holding power measuring ring attached to the specimen. Then, the oven temperature was raised to 0.4 degrees / minute, and the temperature at the time of further drop was recorded.

(8) Evaluation of heat resistance

A 10 g sample was weighed in a test tube and then aged in an oven at 180 ° C. And evaluated by a Gardner color scale after 24 hours. Gardner color has a total of 18 colors and the color of the nearest color is recorded with the naked eye.

(9) Viscosity

A Brookfield viscometer was used. HT-2DB chamber was used and a sample of 10.5 was injected into Spindle No.27. And the stabilization time was 30 minutes after the temperature was raised to the temperature desired for measurement. The viscosity value at which the torque was 50% was recorded starting from the stirring shaft RPM of 0.5.

(10) Softening point

The softening point was measured using the ring and ball softening method (ASTM E 28). The resin was melted into a ring-shaped mold, and the resin was placed in a beaker containing glycerin. The ball was placed in a ring containing the resin, and the temperature was raised by 2.5 ° C per minute to melt the resin (softening point) The results are shown in Table 3.

Experimental Example  3: me-PP based Hot melt  Pressure sensitive adhesive (me-PP based HMPSA , Adhesive A) and measurement of physical properties

20% by weight of a metallocene catalyzed ethylene based polyolefin block copolymer (DOW Chemical), 20% by weight of an oil KL-240 (Minchang Petrochemical Co., Ltd.) and 60% by weight of a petroleum resin used in Examples and Comparative Examples Except that 0.75 part by weight of an antioxidant (Songnox 1010, Songwon Industrial Co., Ltd.) was added to 100 parts by weight of the adhesive of Examples 2, 6, 8, 13 and Comparative Example 1, which were me-PE hot melt pressure sensitive adhesives A (HMPSA).

The preparation conditions were as follows. The ingredients of the above four kinds (petroleum resin, polymer, oil, antioxidant) were added to a 100 ml beaker and stirred at 180 ° C for 4 hours. The detailed weight parts and evaluation results are shown in Table 5. In this case, * Aged in the following table shows the result of measuring each sample after leaving for 3 days at 70 ° C.

The adhesive A of Example 2 The adhesive A of Example 6 The adhesive A of Example 8 The adhesive A of Example 9 The adhesive A The adhesive A of Comparative Example 1 me-PP based
HMPSA composition
(weight%) Hydrogenated petroleum resin
(wt%) Example 2 60 Example 6 60 Example 8 60 Example 9 60 Example 13 60 Comparative Example 1 60 Polymer
(wt%) Infuse 9807 20 20 20 20 20 20 Oil
(wt%) KL-240 20 20 20 20 20 20 Antioxidant Songnox 1010 0.75 parts by weight HMPSA
Properties Softening Point (° C) 103.5 104 104 101 101 103.5 Viscosity
(cps) 160 ° C 5153 5241 5198 5185 3854 4951 180 DEG C 2878 2954 2869 2854 2538 2806 Ball Tack
(Ball No. 9) Initial 9 20 30 15 25 24 * Aged 14 26 40 19 35 34 Peel strength
(gf / in, at SUS) Initial 1952 2107 2366 1852 1260 1285 * Aged 1598 1918 1538 1452 1205 1220 Holding power
(min, 30 DEG C) Initial 682 754 3675 582 135 170 * Aged 542 685 2610 482 105 152 SAFT (占 폚, at SUS, Ramp 0.4 占 폚 / min) Initial 49 51 56 49 45 47 * Aged 49 49 55 48 44 46 Gadner color 180 ℃ * 24 hours 5 5 4 5 7 8 Odor intensity 1.1 1.0 1.0 1.0 2.3 2.4

Experimental Example  4: me- PE  based Hot melt  The pressure-sensitive adhesive (me- PE  based HMPSA , Adhesive B) and measurement of physical properties

20.5% by weight of Exxonmobil chemical Vistamaxx 6202 (metallocene catalyzed polypropylene) and 20% by weight of Evonik Vestoplast 703 (Amorphous propylene-ethylene copolymer), 22.5% by weight of KL-240 Mychang Petrochemical Co., Ltd. as an oil, To the 100 parts by weight of the mixture containing 50 wt% of the used petroleum resin, 0.75 part by weight of an antioxidant (Songnox 1010, Songwon Industrial Co., Ltd.) was added to the mixture to prepare an HMPSA adhesive (me-PP based HMPSA) 13 and Comparative Example 1 were prepared.

The production conditions were as follows. The ingredients of the above four kinds (petroleum resin, polymer, oil, antioxidant) were added to a 100 ml beaker and stirred at 180 ° C for 4 hours. The detailed weight parts and evaluation results are shown in Table 6.

The adhesive B The adhesive B of Example 6 The adhesive B of Example 8 The adhesive B of Example 9 The adhesive B of Example 13 The adhesive B of Comparative Example 1 me-PE based
HMPSA composition
(weight%) Hydrogenated petroleum resin (wt%) Example 2 50 Example 6 50 Example 8 50 Example 9 50 Example 13 50 Comparative Example 1 50 Polymer
(wt%) Vistamaxx 6202 20 20 20 20 20 20 Vestoplast 703 7.5 7.5 7.5 7.5 7.5 7.5 Oil
(wt%) KL-240 22.5 22.5 22.5 22.5 22.5 22.5 Antioxidant Songnox 1010 0.75 parts by weight HMPSA
Properties Softening Point (° C) 89 92 91 90 85 88 Viscosity
(cps) 160 ° C 8950 9152 9080 8502 7521 8065 180 DEG C 4780 5186 5100 4950 3852 4580 Ball Tack
Ball No.9) Initial 11.0 17.0 20 12 11 11.0 * Aged 10 14 25 11 11 12 Peel strength (gf / in, at SUS) Initial 900 1238 1352 850 752 800 * Aged 750 1070 1242 750 582 651 Holding power (min, 30 ℃) Initial 85 141 165 80 68 74 * Aged 66 121 138 60 65 57 SAFT (占 폚, at SUS, Ramp 0.4 占 폚 / min) Initial 42 43 50 41 40 42 * Aged 44 48 49 40 40 45 Gadner color 180 ℃ * 24 hours 6 6 6 7 9 9 Odor intensity 1.4 1.4 1.3 1.4 2.2 1.8

In the table above, * Aged shows the measurement results after each sample was left at 70 ° C for 3 days.

Experimental Example  5: SIS Hot melt  Pressure sensitive adhesive (SIS based HMPSA , Adhesive C) and measurement of physical properties

25 wt% of Kraton polymer SIS D-1161 (Styrene-Isoprene-Styrene Block Cololymer), 18 wt% of KL-240 as an oil (Minchang Petrochemical Company) and 57 wt% of petroleum resin used in Examples and Comparative Examples (HMPSA) of Examples 2, 6, 8, 9, 13 and Comparative Example 1, which are HMPSA adhesives (SIS based HMPSA), were prepared by mixing 0.75 parts by weight of antioxidant Songwox 1010 with 100 parts by weight of the mixture .

The preparation conditions were as follows. The ingredients of the above four kinds (petroleum resin, polymer, oil, antioxidant) were added to a 100 ml beaker and stirred at 180 ° C for 4 hours. The detailed weight parts and evaluation results are shown in Table 7.

　
　
　 The adhesive C of Example 2 The adhesive C of Example 6 The adhesive C of Example 8 The adhesive C of Example 9 The adhesive C of Example 13 The adhesive C of Comparative Example 1

SIS based HMPSA composition (% by weight)


Hydrogenated petroleum resin (wt%) Example 2 57 Example 6 57 Example 8 57 Example 9 57 Example 13 57 Comparative Example 1 57 Polymer (wt%) SIS D-1161 25 25 25 25 25 25 Oil (wt%) KL-240 18 18 18 18 18 18 Antioxidant Songnox 1010 0.75 parts by weight




HMPSA Properties





Softening Point (° C) 103.5 104 104 102 101 103.5 Viscosity (cps) 160 ° C 5153 5241 5198 4952 3854 4951 180 DEG C 2878 2954 2869 2752 2538 2806 Ball Tack (Ball No.9) Initial 5.1 8.4 10.5 8 6.5 6.4 * Aged 8.1 12.6 17 13 8.1 8.3 Peel strength (gf / in, at SUS) Initial 1338 1718 1958 1352 1310 1332 * Aged 1355 1353 1524 1405 1398 1438 Holding power (min, 30 ℃) Initial 1020 1920 2554 592 293 383 * Aged 2054 3396 3514 1155 538 674 SAFT (占 폚, at SUS, Ramp 0.4 占 폚 / min) Initial 53 56 68 50 49 51 * Aged 62 64 65 51 52 56 Gadner color 180 ℃ * 24 hours 6 6 5 6 9 10 Odor intensity 1.5 1.1 1.1 1.6 3.5 3

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

PE-based adhesive was prepared by mixing 40 wt% of Dow chemical Affinity 1950GA (metallocene catalyzed poly ethylene), 20 wt% of Sasol C-80 (wax) and 40 wt% of petroleum resin used in Examples and Comparative Examples HMA) of Examples 2, 6, 7, 8, 13 and Comparative Examples 1, 2 and 4 were prepared.

The preparation conditions were as follows. The four kinds of raw materials were added to a 100 ml beaker and stirred at 180 ° C for 1 hour. The detailed weight parts and evaluation results of properties are shown in Table 8.

The adhesive D of Example 2 The adhesive D of Example 6 The adhesive D of Example 7 The adhesive D of Example 8 The adhesive D of Example 13 The adhesive D of Comparative Example 1 The adhesive D of Comparative Example 2 The adhesive D of Comparative Example 4 me-PE based
HMA composition
(weight%)
Hydrogenated petroleum resin Example 2 40 Example 6 40 Example 7 40 Example 8 40 Example 13 40 Comparative Example 1 40 Comparative Example 2 40 Comparative Example 4 40 Polymer Affinity 1950 GA 40 40 40 40 40 40 40 40 Wax Sasol C-80 20 20 20 20 20 20 20 20 HMA Softening Point (° C) 87.7 89 89 88.9 85 89.2 91 89 Properties Viscosity
(cps) 160 ° C 1641 1750 1685 1670 1258 1718 1952 1718 180 DEG C 996 1120 1054 1026 850 1046 1125 1046 Adhesion properties Hardness
(HAD) 38 38 38 39 35 32 35 32 Open time
(sec) 18 18 18 19 13 14 15 16 Set time
(sec) 0.7 0.6 0.5 0.5 1.5 0.9 1.2 1.2 Thermal properties Gadner color 180 ℃ * 24 hours 7 7 7 7 10 10 9 10 Odor intensity 1.3 1.1 1.1 1.0 3.5 3 3.3 2.1

Experimental Example  7: EVA Hot melt  glue( EVA  based HMA , Adhesive E) and measurement of physical properties

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

The preparation conditions were as follows. The four kinds of raw materials were added to a 100 ml beaker and stirred at 180 ° C for 1 hour. The detailed weight parts and evaluation results of the properties are shown in Table 9.

The adhesive E of Example 2 The adhesive E of Example 6 The adhesive E of Example 7 The adhesive E of Example 8 The adhesive E of Example 13 The adhesive E of Comparative Example 1 The adhesive E of Comparative Example 2 The adhesive E of Comparative Example 4 EVA
based
HMA composition
(weight%) Hydrogenated petroleum resin Example 2 40 Example 6 40 Example 7 40 Example 8 40 Example 13 40 Comparative Example 1 40 Comparative Example 2 40 Comparative Example 4 40 Polymer EVA (28/400) 40 40 40 40 40 40 40 40 Wax Sasol C-80 20 20 20 20 20 20 20 20 HMA
Properties Softening Point (° C) 89.5 91.4 89 88.9 87 89.2 92 89 Viscosity
(cps) 160 ° C 1250 1719 1685 1685 1190 1195 1684 1210 180 DEG C 688 1040 958 987 587 589 1021 595 Adhesion properties Hardness
(HAD) 72 74 73 73 72 72 75 75 Open time
(sec) 16 15 15 17 14 14 14 13 Set time
(sec) 0.5 0.6 0.8 0.9 One 0.9 0.9 1.2 Thermal properties Gadner color 180 ℃ * 24 hours 8 7 7 7 9 11 9 9 Odor intensity 3.8 3.5 3.5 3.5 4.9 4.8 4.5 4.2

Experimental Example  8: APAO Hot melt  glue( EVA  based HMA , Adhesive F) and measurement of physical properties

(APAO based HMA) was prepared by mixing 40 wt% of an amorphous propylene-ethylene copolymer of Evonik 703 (Evonik), 20 wt% of Sasol C-80 (Sasol) with 40 wt% of petroleum resin used in Examples and Comparative Examples, (HMA) of Examples 2, 6, 7, 8, 13 and Comparative Examples 1, 2 and 4 were prepared.

The preparation conditions were as follows. The four kinds of raw materials were added to a 100 ml beaker and stirred at 180 ° C for 1 hour. The detailed weight parts and evaluation results of the properties are shown in Table 10.

The adhesive F of Example 2 The adhesive F of Example 6 The adhesive F of Example 7 The adhesive F of Example 8 The adhesive F of Example 13 The adhesive F of Comparative Example 1 The adhesive F of Comparative Example 2 The adhesive F of Comparative Example 4 APAO
based
HMA composition
(weight%) Hydrogenated oil
Suzy Example 2 40 Example 6 40 Example 7 40 Example 8 40 Example 13 40 Comparative Example 1 40 Comparative Example 2 40 Comparative Example 4 40 Polymer Vestoplast703 40 40 40 40 40 40 40 40 Wax Sasol C-80 20 20 20 20 20 20 20 20 HMA
Properties Softening Point (° C) 99 100 99 100 99 99 101 99 Melt
Viscosity
(cps) 160 ° C 525 521 525 579 495 512 605 511 180 DEG C 310 352 325 364 284 305 351 302 Adhesion properties Hardness
(HAD) 38 41 40 39 35 32 34 32 Open time
(sec) 16 18 17 18 12 12 12 13 Set time
(sec) 0.8 0.8 0.8 0.9 One 0.9 0.9 1.2 Thermal properties Gadner color 180 ℃ * 24 hours 7 7 7 7 8 11 9 11 Odor intensity 2.5 2.8 2.7 2.9 4.0 4.1 4.0 3.5

Through the adhesives A to F, it can be confirmed that the adhesive of the present invention has an increased adhesive force, improved odor, and improved heat resistance.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the actual scope of the present invention will be defined by the claims of the appended claims and their equivalents.

Claims (21)

A hydrogenated petroleum resin comprising repeating units represented by the following formulas (1) and (2):
[Chemical Formula 1]

(2)

(Wherein R ₁ is H or a methyl group, R ₂ is a C ₁ to C 18 alkyl group, 0? M? 10, and 0? N? 10) The method according to claim 1,
Wherein R ₁ is H and R ₂ is 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. Suzy. The method according to claim 1,
Wherein R ₁ is H and R ₂ is 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. The method according to claim 1,
Wherein the hydrogenated petroleum resin comprises 60 to 90 mol% of the repeating unit represented by the formula (1) and 10 to 40 mol% of the repeating unit represented by the formula (2). The method according to claim 1,
Wherein the hydrogenated petroleum resin has a peak area of 0.8 to 1.0 ppm relative to a peak area of 1.4 to 7.5 ppm in the NMR spectrum obtained after ¹ H-NMR measurement of not less than 0.2. The method according to claim 1,
Wherein the hydrogenated petroleum resin has a peak area of 1.0 to 1.4 ppm relative to a peak area of 1.4 to 7.5 ppm in the NMR spectrum obtained after ¹ H-NMR measurement of 0.5 or more. The method according to claim 1,
The hydrogenated petroleum resin has a peak area of 0.8 to 1.0 ppm relative to a peak area of 1.4 to 7.5 ppm in the NMR spectrum obtained after ¹ H-NMR measurement of 0.2 to 0.8 and a peak area of 1.0 to 1.4 ppm relative to a peak area of 1.4 to 7.5 ppm Wherein the peak area is 0.5 to 0.8. The method according to claim 1,
In the NMR spectrum obtained after ¹ H-NMR measurement of the hydrogenated petroleum resin,
Wherein the hydrogenated petroleum resin has a full width at half maximum (FWHM) at a peak of 0.85 ppm of not more than 0.1 ppm. The method according to claim 1,
In the NMR spectrum obtained after ¹ H-NMR measurement of the hydrogenated petroleum resin,
Wherein the full width at half maximum of the 1.20 ppm peak is 0.4 ppm or less. The method according to claim 1,
In the NMR spectrum obtained after ¹ H-NMR measurement of the hydrogenated petroleum resin,
Wherein 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 according to claim 1,
Wherein the hydrogenated petroleum resin has a weight average molecular weight of 500 to 3,000 g / mol, a softening point of 90 to 150 캜, and a color (APHA color) of 1 to 100. Preparing a petroleum resin by thermally polymerizing dicyclopendadiene and a C3 to C20 olefin monomer; And
And performing a hydrogenation reaction of the petroleum resin with a hydrogenation catalyst. 13. The method of claim 12,
Wherein the olefin-based monomer is a linear or branched alpha-olefin-based monomer. 14. The method of claim 13,
The linear alpha olefin monomer may be selected from the group consisting of propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, Wherein the hydrogenated petroleum resin is one selected from the group consisting of hexadecene, 1-octene, and combinations thereof. 14. The method of claim 13,
The branched alpha- olefin-based monomer may be at least one selected from the group consisting of isobutylene, 3-methyl-1-butene, 2-methyl-1-butene, Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, -1-pentene, and a combination thereof. The method for producing a hydrogenated petroleum resin according to claim 1, 13. The method of claim 12,
Wherein the thermal polymerization is carried out at a temperature of 200 to 320 캜. 13. The method of claim 12,
Wherein the hydrogenation catalyst is at least one selected from the group consisting of nickel, palladium, cobalt, platinum and rhodium catalysts. 13. The method of claim 12,
Wherein the hydrogenation reaction is carried out at a temperature of 150 to 300 DEG C under a pressure of 50 to 150 bar. A bonding composition comprising the hydrogenated petroleum resin according to any one of claims 1 to 11. 20. The method of claim 19,
Wherein the adhesive composition comprises at least one of a base polymer, a wax, and an oil. 20. The method of claim 19,
Wherein the adhesive composition has a softening point of 50 to 150 占 폚, a melt viscosity of 300 to 10,000 cps at 160 占 폚, and a viscosity of 200 to 8,000 cps at 180 占 폚.

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