Resin composition, its manufacturing method, and coating composition containing the same

Abstract

The present invention relates to a resin composition comprising a modified petroleum resin having a structure in which a molecular weight regulator is bonded to at least one of both ends of an at least partially hydrogenated or non-hydrogenated petroleum resin, the modified petroleum resin containing at least one unit structure derived from a styrene monomer and having a Gardner color number of 10 or less.

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a method for producing the same, and a coating composition and a paint composition containing the same. [Background technology]

[0002] Paints are manufactured by blending the main materials, resin, hardener, solvent, pigment, and other additives. Well-known paint resins include polyester, epoxy, and acrylic resins, and an appropriate resin can be selected and used depending on the application and method of use.

[0003] Paints can be used in a variety of fields, such as wall painting, traffic line (traffic painting), ship coating, and metal aggregate coating. Depending on the application, paints must be resistant to temperature changes during application and weather resistance after application. In particular, in the case of ship paints, the inclusion of inorganic particles, such as talc and ceramic particles, as additives increases viscosity, resulting in reduced paint flexibility and the occurrence of cracks or separation in the coating film after application. To address this issue, various diluents have been researched, but there remains a need for a diluent that can sufficiently reduce paint viscosity and sufficiently increase adhesion.

[0004] Furthermore, low viscosity resins recently developed for use as diluents are colored, and there remains a problem that color changes due to the resin occur during paint production.

[0005] Thus, there remains a need for a substantially clear, low viscosity resin that not only imparts low viscosity to paints, but also does not cause color shift and has improved hue. Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a resin composition which has a low viscosity and at the same time has a Gardner color scale of 10 or less, and a paint and a rubber composition for tires which contain the same. [Means for solving the problem]

[0007] According to one embodiment, the present invention provides a modified petroleum resin having a structure in which a molecular weight regulator is bound to at least one of both ends of an at least partially hydrogenated or non-hydrogenated petroleum resin, the modified petroleum resin comprising at least one unit structure derived from a styrene monomer, A resin composition having a Gardner color scale of 10 or less is provided.

[0008] According to another aspect, there is provided a paint comprising the resin composition.

[0009] According to yet another aspect, there is provided a paint comprising the coating material.

[0010] According to yet another aspect, there is provided a method for producing a resin composition, the method comprising the step of adding a polymerization catalyst and / or heat to a solution containing one or more of a C5 monomer, a C5 mixed fraction, a C9 monomer, a C9 mixed fraction, a cyclic diolefin monomer, and a linear olefin monomer, and a molecular weight modifier, to carry out a polymerization reaction, and obtaining a polymerization reaction product, The method for producing the resin composition is provided, wherein the resin composition has a Gardner color scale of 10 or less. [Effects of the Invention]

[0011] The coating material of the present invention contains a low-viscosity resin composition having a Gardner color scale of 10 or less, which not only imparts low viscosity to the paint but also improves color tone, and has excellent compatibility with tire rubber, resulting in advantageous advantages such as improved tire braking, fuel economy, and wear resistance. DETAILED DESCRIPTION OF THE INVENTION

[0012] Various aspects and embodiments of the present invention will be described in more detail below.

[0013] As used herein, "petroleum resin" includes polymers of one or more of a C5 monomer, a C5 mixed fraction, a C9 monomer, a C9 mixed fraction, a cyclic diolefin monomer, and a linear olefin monomer. For example, the petroleum resin includes homopolymers and copolymers. Examples of the petroleum resin homopolymer include a polymer of a C5 monomer, a polymer of a C5 mixed fraction, a polymer of a C9 monomer, a polymer of a C9 mixed fraction, a polymer of a cyclic diolefin monomer, and a polymer of a linear olefin monomer. Examples of the petroleum resin copolymer include copolymers of two different C5 monomers, copolymers of two different C9 monomers, copolymers of two different cyclic diolefin monomers, copolymers of two different linear olefin monomers, copolymers of a C5 fraction and a C5 monomer, copolymers of a C5 fraction and a C9 monomer, copolymers of a C9 fraction and a C5 monomer, copolymers of a C5 monomer and a C9 monomer, copolymers of a C9 fraction and a C5 monomer, copolymers of a C5 monomer and a C9 monomer, copolymers of a C9 fraction and a C9 monomer, copolymers of a C5 fraction and a linear olefin monomer, copolymers of a C9 fraction and a linear olefin monomer, copolymers of a C5 fraction and a cyclic diolefin monomer, copolymers of a C9 fraction and a cyclic diolefin monomer, copolymers of a C5 monomer and a cyclic diolefin monomer, copolymers of a C9 monomer and a linear olefin monomer, and copolymers of a cyclic diolefin monomer and a linear olefin monomer.

[0014] In this specification, the term "hydrogenated petroleum resin" refers to the above-mentioned petroleum resin in which at least a portion of unsaturated moieties such as ethylene has been modified to saturated hydrocarbons by a hydrogenation reaction.

[0015] As used herein, the term "C5 (mixed) fraction" refers to aliphatic C5 derived from naphtha cracking, as well as C6 paraffins, C6 olefins, and C6 diolefins. For example, the C5 fraction may include, but is not limited to, pentene, isoprene, 2-methyl-2-butene, 2-methyl-2-pentene, cyclopentadiene, and piperylene, and may also include mixtures of two or more of the C5 monomers. The C5 fraction may also be selectively alkylated.

[0016] In this specification, the term "C5 monomer" refers to any one of the components contained in the aforementioned C5 (mixed) fraction.

[0017] As used herein, the term "C9 (mixed) fraction" refers to a composition derived from petroleum processing, e.g., cracking, that boils at atmospheric pressure and between about 100°C and 300°C, as is generally understood in the art to which the present invention pertains. 10 The C9 fraction may include olefin species, such as, but not limited to, vinyltoluene, α-methylstyrene, styrene, dicyclopentadiene, indene, trans-β-methylstyrene, and methylindene, and may also include mixtures of two or more of the C9 monomers. The C9 fraction may also be selectively alkylated. For example, the C9 fraction in the present invention may include vinyltoluene, indene, styrene, dicyclopentadiene, and alkylated derivatives of these components, such as α-methylstyrene and methylindene.

[0018] As used herein, the term "C9 monomer" refers to any one of the components contained in the aforementioned C9 fraction.

[0019] As used herein, "olefin" includes unsaturated compounds containing at least one ethylenically unsaturated (C=C) bond. For example, the olefin may include, but is not limited to, linear olefins, cyclic olefins, α-olefins, etc.

[0020] As used herein, "cyclic diolefin" includes cyclic saturated compounds containing two C=C bonds. For example, the cyclic diolefin can include, but is not limited to, dicyclopentadiene, tricyclopentadiene, and the like.

[0021] One aspect of the present invention relates to a method for producing a resin composition, which includes the step of adding a polymerization catalyst and / or heat to a solution containing one or more of a C5 monomer, a C5 mixed fraction, a C9 monomer, a C9 mixed fraction, a cyclic diolefin monomer, and a linear olefin monomer, and a molecular weight regulator to perform a polymerization reaction, thereby obtaining a polymerization reaction product, wherein the polymerization reaction product contains at least one unit structure derived from a styrene monomer and has a Gardner color scale of 10 or less.

[0022] According to an embodiment, the solution may further include a viscosity modifier, which facilitates adjustment of the viscosity of the polymerization reaction product.

[0023] The viscosity modifier does not participate in the formation of the structure of the product polymer, but serves to adjust the viscosity of the reactants and the product. Therefore, according to the present invention, a polymerization catalyst and / or heat is added to a solution containing one or more of a C5 monomer, a C5 mixed fraction, a C9 monomer, a C9 mixed fraction, a cyclic diolefin monomer, and a linear olefin monomer, a molecular weight modifier, and a viscosity modifier to carry out a polymerization reaction, and the resulting polymerization reaction product may be a mixture of a modified polymer and a viscosity modifier.

[0024] According to one embodiment, the solution may further include a styrene monomer and a xylene solvent. Here, the styrene monomer refers to pure styrene monomer. The petroleum resin obtained thereby has a Gardner color scale of 10 or less. For example, the Gardner color scale may be 0 to 10, 1 to 10, 1 to 10, 3 to 10, or 4 to 10.

[0025] According to an embodiment, the method may further include a step of converting the petroleum resin into a hydrogenated petroleum resin by hydrotreating in the presence of a catalyst.

[0026] The catalyst used in the hydrotreating process may be a hydrogenation catalyst well known in the petroleum resin field, such as Pd, Ni, Pt, or a mixture thereof.

[0027] According to an embodiment, the xylene solvent may be added to prevent degradation of processability due to increased monomer density associated with the addition of styrene monomer. For example, the styrene monomer and the xylene solvent may be added to the solution in a ratio of 4:1 to 1:1 by weight. For example, the styrene monomer and the xylene solvent may be added to the solution in a ratio of 3:1 to 1:1, 3:1 to 1.2:1, 2.5:1 to 1.2:1, or 2.3:1 to 1.2:1 by weight.

[0028] In addition, the xylene solvent is added to adjust the monomer concentration in the polymerization system, which is increased by adding pure styrene monomer, and the addition of the xylene solvent can prevent heat generation due to an increase in the monomer concentration during polymerization.

[0029] According to one embodiment, the molecular weight modifier may be included in an amount of more than 0 to 15 parts by weight per 100 parts by weight of the total resin composition, and the viscosity modifier may be included in an amount of more than 0 to 40 parts by weight per 100 parts by weight of the total resin composition.

[0030] For example, the molecular weight regulator may be included in an amount of 1 to 10 parts by weight, 1 to 5 parts by weight, 1 to 2.5 parts by weight, or 1 to 1.4 parts by weight.

[0031] For example, the viscosity modifier may be included in an amount of 10 to 30 parts by weight, or 15 to 25 parts by weight.

[0032] When the contents of the molecular weight modifier and viscosity modifier satisfy the above ranges, it is possible to produce a low-viscosity petroleum resin that has good compatibility with paint raw materials. Without the molecular weight modifier, a high-molecular-weight and high-viscosity petroleum resin is obtained. If the amount exceeds 15 parts by weight, the viscosity becomes too low, resulting in poor paintability of the final product (e.g., paint). The viscosity modifier is added to lower the viscosity of the modified petroleum resin and can be added as needed. However, if the amount exceeds 40 parts by weight, the viscosity becomes too low, resulting in poor paintability of the final product (e.g., paint). Therefore, the molecular weight modifier and viscosity modifier must be blended in an appropriate ratio.

[0033] According to one embodiment, the molecular weight regulator usable in the present invention is a chain transfer agent, and examples thereof include thiols or halocarbons such as carbon tetrachloride.

[0034] For example, the thiols, i.e., organic mercaptan molecular weight regulators containing one or more thiol groups (—SH), are useful, including aliphatic mercaptans, cycloaliphatic mercaptans, or aromatic mercaptans.

[0035] Such mercaptans may contain 1 to 4 thiol groups per molecule, and 1 to 20 carbons, preferably 1 to 15 carbons, per thiol group.

[0036] In addition to the hydrocarbon group and the thiol group, other substituents may be added, and examples of such substituents include a hydroxy group, a carboxylic acid group, an ether group, an ester group, a sulfide group, an amine group, an amide group, and the like.

[0037] In the present invention, the mercaptans useful as molecular weight regulators are not particularly limited as long as they are organic compounds having a thiol group, and specific examples include alkyl mercaptans such as ethyl mercaptan, butyl mercaptan, hexyl mercaptan, octyl mercaptan, and dodecyl mercaptan; thiolphenols such as phenyl mercaptan and benzyl mercaptan; hydroxyl group- or carboxylic acid group-containing mercaptans such as 2-mercaptoethanol, thioglycolic acid, and 3-mercaptopropionic acid; mercaptans having two or more functional groups such as pentaerythritol tetrakis(3-mercapto)propionate; and mixtures of two or more of these.

[0038] Specific examples of such mercaptans include, but are not limited to, methyl mercaptan, ethyl mercaptan, butyl mercaptan, octyl mercaptan, lauryl mercaptan, mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, benzyl mercaptan, phenyl mercaptan, cyclohexyl mercaptan, 1-thioglycerol, 2,2'-dimercaptodiethyl ether, 2,2'-dimercaptodipropyl ether, 2,2'-dimercaptodiisopropyl ether, 3,3'-dimercaptodipropyl ether, 2,2'-dimercaptodiethyl sulfide, 3,3'-dimercaptodipropyl sulfide, bis(β-mercaptoethoxy)methane, bis(β-mercaptoethylthio)methane, trimethylolpropane trithioglycolate, pentaerythritol tetrathioglycolate, and the like.

[0039] According to one embodiment, the molecular weight regulator of the present invention includes ethyl mercaptan, butyl mercaptan, hexyl mercaptan, octyl mercaptan, dodecyl mercaptan; phenyl mercaptan, benzyl mercaptan; mercaptoethanol, thiol glycolic acid, mercaptopropionic acid; and pentaerythritol tetrakis(3-mercapto)propionate.

[0040] For example, in the present invention, the effect of molecular weight control can be maximized by using n-dodecyl mercaptan of the following Chemical Formula 1, 2-mercaptoethanol of the following Chemical Formula 2, or a mixture thereof as a molecular weight control agent.

[0041] [ka]

[0042] [ka]

[0043] According to one embodiment, the viscosity modifier may be a low-viscosity liquid resin having a viscosity (25°C) of 20 to 500 cps. Any liquid resin satisfying the viscosity requirement may be used as a viscosity modifier for a resin composition according to one embodiment of the present invention without any particular limitation.

[0044] For example, the low viscosity liquid resin may be selected from hydrogenated DCPD-C9 copolymer resin, hydrogenated DCPD resin, and a mixture thereof.

[0045] Here, the hydrogenated dicyclopentadiene (DCPD)-C9 copolymer resin means a white thermoplastic resin obtained through polymerization and hydrogenation of dicyclopentadiene (DCPD). As such a hydrogenated dicyclopentadiene (DCPD)-C9 copolymer resin, SUKOREZ TMCommercially available resins such as resins can also be used.

[0046] For example, by using a hydrogenated dicyclopentadiene (DCPD)-C9 copolymer resin having the following structure as a viscosity modifier, the effects of viscosity control and improvement of anti-air permeability can be maximized.

[0047] [ka]

[0048] According to an embodiment, the polymerization catalyst may be selected from the group consisting of Lewis acid catalysts, halohydric acids, AlCl3, BF3, and mixtures of two or more thereof.

[0049] Preferably, the polymerization catalyst is a Lewis acid catalyst selected from AlCl3, BF3, SnCl4, TiCl4, AgClO4, I2, and a mixture of two or more thereof.

[0050] According to one embodiment, the application of heat may be performed by increasing the temperature to 100°C to 300°C.

[0051] One aspect of the present invention relates to a resin composition comprising a modified petroleum resin having a structure in which a molecular weight regulator is bound to at least one of both ends of an at least partially hydrogenated or non-hydrogenated petroleum resin, the modified petroleum resin containing at least one unit structure derived from a styrene monomer and having a Gardner color scale of 10 or less.

[0052] According to an embodiment, the petroleum resin or hydrogenated petroleum resin may include a styrene monomer as a polymerization raw material.

[0053] Here, the styrene monomer refers to pure styrene monomer, and the inclusion of such pure styrene monomer as a polymerization raw material has the effect of improving the color of the petroleum resin. For example, the modified petroleum resin may have a Gardner color scale of more than 0 but not more than 10, or from 1 to 10. This not only prevents color change in paints containing the resin composition, but also reduces the amount of pigment added for whitening, which is economically advantageous.

[0054] According to an embodiment, the styrene monomer-derived unit structure may be contained in an amount of more than 0 to less than 100 parts by weight per 100 parts by weight of the modified petroleum resin.

[0055] For example, the styrene monomer-derived unit structure may be present in an amount of 13 to 95 parts by weight, 15 to 90 parts by weight, 20 to 85 parts by weight, or 27 to 80 parts by weight per 100 parts by weight of the modified petroleum resin, but is not limited thereto.

[0056] According to one embodiment, the modified petroleum resin is a modified petroleum resin in which one or more of the C5 monomer, C5 mixed fraction, C9 monomer, C9 mixed fraction, cyclic diolefin monomer, and linear olefin monomer are polymerized, and at least a portion of the hydrogenated or non-hydrogenated petroleum resin is modified with the molecular weight modifier. Since the modified petroleum resin contains a unit structure derived from a styrene monomer, the resulting petroleum resin has a lower Gardner color index, for example, a Gardner color index of 10 or less, compared to existing petroleum resins that do not contain a unit structure derived from a styrene monomer.

[0057] According to one embodiment, the modified petroleum resin has a structure in which one or more of the C5 monomer, C5 mixed fraction, C9 monomer, C9 mixed fraction, cyclic diolefin monomer, and linear olefin monomer are polymerized through an addition polymerization reaction or a chain polymerization reaction, and the molecular weight regulator is bound to at least one of both ends of at least a portion of a hydrogenated or non-hydrogenated petroleum resin.

[0058] For example, the petroleum resin contains at least one unit structure derived from a C9 mixed fraction, or is also composed of repeating units derived from a C9 mixed fraction.

[0059] According to one embodiment, the unit structure derived from the C9 mixed fraction may include vinyltoluene, α-methylstyrene, styrene, dicyclopentadiene, indene, and methylindene.

[0060] According to one embodiment, the petroleum resin may include a structure in which repeating units represented by the following Formula 4a, 4b, or 4c are bonded: Here, although not specifically shown, the petroleum resin may have repeating units derived from styrene monomers that account for 60% to 95%, for example, 75% to 95%, of the repeating units contained in the petroleum resin.

[0061] According to one embodiment, the petroleum resin comprises a structure in which repeating units such as those represented by the following formula 4a are bonded: For example, the petroleum resin may comprise the following structure formed by polymerization of styrene, α-methylstyrene, vinyltoluene, indene, methylindene, dicyclopentadiene, and alkylated derivative monomers of these components, such as α-methylstyrene and methylindene, contained in the C9 mixed fraction.

[0062] [ka]

[0063] The above formula 4a is merely an example, and other C5 monomers, C9 monomers, cyclic diolefin monomers, and linear olefin monomers not shown in the structure may also be included as repeating units.

[0064] For example, the petroleum resin is a polymer containing the above structure, and the polymer means a random polymer, but is not limited thereto, and also includes a block copolymer or an alternating copolymer.

[0065] Although not shown separately, the petroleum resin may include a structure in which at least one of the repeating units represented by Formula 4a is hydrogenated.

[0066] According to another embodiment, the petroleum resin may have a structure in which the following repeating units are bonded: For example, the petroleum resin may have a structure in which at least one of both ends has a double bond, and a structure in which both ends have double bonds is exemplarily represented by the following chemical formula 4b:

[0067] [ka]

[0068] In this way, a molecular weight modifier is bonded to the double bond located at at least one end to form a petroleum resin (e.g., a polymer of C9 monomers) modified with the molecular weight modifier. The molecular weight modifier can be bonded to either end, or to only one end, as shown in the following exemplary formula 4c:

[0069] Although not shown separately, the petroleum resin may include a structure in which at least one of the repeating units represented by Formula 4b or 4c is hydrogenated.

[0070] [ka]

[0071] According to one embodiment, the resin composition may have a number average molecular weight (Mn) of 200 to 400, a weight average molecular weight (Mw) of 400 to 700, a Z-average molecular weight (Mz) of 650 to 5,000, and a polydispersity (MWD) of 1 to 3. Desirably, the resin composition may have a number average molecular weight (Mn) of 200 to 350, a weight average molecular weight (Mw) of 400 to 570, a Z-average molecular weight (Mz) of 650 to 5,000, and a polydispersity (MWD) of 1.5 to 3.

[0072] If the number average molecular weight is lower than 200, there is a problem of low compounding efficiency, and if it is higher than 400, compounding processability is reduced. In addition, such a low molecular weight range provides excellent processability and can be applied to low viscosity paints, which allows for the application of excellent coating films.

[0073] According to one embodiment, the resin composition has a viscosity of 5,000 to 50,000 cps at 25°C and a glass transition temperature of -40°C to -25°C.

[0074] If the glass transition temperature is lower than -40°C, not only will the resin composition be highly volatile, but the low viscosity will also result in poor paintability. If the glass transition temperature is higher than -25°C, the viscosity of the paint produced using the resin composition will not be low enough, resulting in poor processability and insufficient flexibility, which will cause cracks in the paint.

[0075] According to an embodiment, the resin composition may further include a viscosity modifier.

[0076] According to one embodiment, the viscosity modifier may be included in an amount of more than 0 and less than or equal to 40 parts by weight per 100 parts by weight of the resin composition.

[0077] As described above, when the modified petroleum resin according to an embodiment of the present invention further comprises a viscosity modifier, it can be obtained by carrying out a polymerization reaction by adding a polymerization catalyst and / or heat to a solution containing one or more of a C5 monomer, a C5 mixed fraction, a C9 monomer, a C9 mixed fraction, a cyclic diolefin monomer, and a linear olefin monomer, a molecular weight modifier, and a viscosity modifier. However, the viscosity modifier does not participate in the structure formation of the modified petroleum resin product, but serves to adjust the viscosity of the reactants and the product, so the polymerization reaction product may be a mixture of the modified polymer and the viscosity modifier.

[0078] The C5 monomer, C5 mixed fraction, C9 monomer, C9 mixed fraction, cyclic diolefin monomer, linear olefin monomer, and pure styrene monomer are described above, and various specific examples such as molecular weight modifiers and viscosity modifiers are described above.

[0079] According to one embodiment, the resin composition has a viscosity measured at 25° C. of 5,000 to 50,000 cps, for example, 5,000 to 17,000 cps, or 5,000 to 15,000 cps.

[0080] The aromaticity is between 25% and 70%, for example between 30% and 60%, or between 35% and 50%.

[0081] When the aromaticity range is satisfied, sufficient compatibility with the coating material is obtained, making it possible to form a coating that is excellent in workability and durability.

[0082] One aspect of the present invention relates to a coating composition containing a resin composition.

[0083] According to one embodiment, the coating composition may include a base resin, the resin composition, a curing agent, a curing accelerator, a pigment, an additive, and a solvent.

[0084] The coating composition may be free of plasticizers by using a low viscosity resin composition.

[0085] According to an embodiment, the base resin may include an epoxy resin.

[0086] According to an embodiment, the curing agent may include a known heat-curing agent, a photo-curing agent, or a UV-curing agent, and may be appropriately selected depending on the application.

[0087] According to an embodiment, the curing accelerator is added to adjust the curing speed of the curing agent, and may be appropriately selected from known curing accelerators, including sulfonic acid curing catalysts and carbamate curing catalysts, as needed.

[0088] According to one embodiment, the pigment is added to the coating composition to provide color or improve whiteness, and may include, but is not limited to, inorganic pigments such as titanium dioxide. Any known pigment may be appropriately selected and used. For example, the resin composition according to one embodiment of the present invention may have a Gardner color scale of 10 or less, e.g., 1 to 10, thereby reducing the amount of pigment added, thereby improving economic efficiency.

[0089] According to one embodiment, the additives may include all components that can be incorporated into paints, excluding curing agents, curing accelerators, pigments, and solvents. For example, the additives may include surface conditioners, light stabilizers, weathering additives, preservatives, appearance control agents, defoamers, leveling agents, or combinations thereof. Such additives may be appropriately selected from known materials.

[0090] According to an embodiment, the solvent may be selected from solvents that have good miscibility with the coating material, for example, an organic solvent may be used.

[0091] The raw materials to be blended into the above-mentioned coating composition can be appropriately blended by a person skilled in the art, taking into consideration the intended use, desired viscosity, color, etc., and referring to known compositions.

[0092] One aspect of the present invention relates to a rubber composition comprising a raw rubber and a resin composition according to various embodiments of the present invention.

[0093] According to an embodiment, the rubber composition may further include at least one of raw rubber, a reinforcing agent, a silane coupling agent, a vulcanization agent, and a vulcanization accelerator, in addition to the modified petroleum resin and the viscosity modifier.

[0094] The raw rubber may include natural rubber, synthetic rubber, or a combination thereof having olefinic double bonds.

[0095] The raw rubber is not particularly limited as long as it has an olefinic double bond (carbon-carbon double bond), and natural rubber, synthetic rubber, or a mixture thereof can be used.

[0096] For example, the raw rubber may include at least one selected from the group consisting of natural rubber, butadiene rubber, nitrile rubber, silicone rubber, isoprene rubber, styrene-butadiene rubber (SBR), isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, acrylonitrile-butadiene rubber (NBR), ethylene-propylene-diene rubber, halogenated butyl rubber, halogenated isoprene rubber, halogenated isobutylene copolymer, chloroprene rubber, butyl rubber, and halogenated isobutylene-p-methylstyrene rubber.

[0097] The reinforcing agent may include carbon black and silica.

[0098] By including carbon black, the rubber composition can obtain effects such as improved abrasion resistance, improved rotation resistance, and prevention of cracks and cracks caused by ultraviolet rays (prevention of ultraviolet degradation). There are no particular limitations on the carbon black that can be used in the present invention, and any carbon black commonly used in the technical field can be used.

[0099] According to an embodiment, the carbon black may include furnace black, acetylene black, thermal black, channel black, graphite, or a combination thereof.

[0100] For example, the physical properties of the carbon black, such as particle size, pore volume, and specific surface area, are not particularly limited, and may include various carbon blacks conventionally used in the rubber industry, such as SAF, ISAF, HAF, FEF, GPF, and SRF (all of which are abbreviations for carbon blacks classified in accordance with the US ASTM standard D-1765-82a).

[0101] The silica may be any silica used as a reinforcing agent for rubber, without any particular limitation, and examples thereof include dry process white carbon, wet process white carbon, synthetic silicate white carbon, colloidal silica, precipitated silica, etc. The specific surface area of ​​the silica is not particularly limited, but is usually 40 to 600 m 2 / g range, e.g., 70 to 300 m 2 / g, and those having a primary particle diameter of 10 to 1,000 nm can be used. They may be used alone or in combination of two or more.

[0102] As the reinforcing agent, in addition to the above-mentioned carbon black and silica, mineral powders such as clay and talc; carbonates such as magnesium carbonate and calcium carbonate; alumina hydrates such as aluminum hydroxide, etc. can be used.

[0103] According to one embodiment, the silane coupling agent is used to incorporate silica, and may be selected from the group consisting of vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, bis(3-(triethoxysilyl)propyl)disulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-(triethoxysilyl)propyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyl The silane may comprise trimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, or combinations thereof. For example, the silane coupling agent may include bis(3-(triethoxysilyl)propyl)tetrasulfide.

[0104] Along with the crosslinking agent, the rubber composition for a tire tread according to the present invention may also contain a vulcanization accelerator or vulcanization aid.

[0105] According to an embodiment, the vulcanization accelerator and the vulcanization aid are not particularly limited and may be appropriately selected depending on the rubber component, isobutylene polymer, and crosslinking agent contained in the rubber composition. Furthermore, "vulcanization" refers to crosslinking involving at least one sulfur atom.

[0106] Examples of the vulcanization accelerator include thiuram accelerators such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, and tetraethylthiuram disulfide; thiazole accelerators such as 2-mercaptobenzothiazole and dibenzothiazyl disulfide; sulfenamide accelerators such as N-cyclohexyl-2-benzothiazylsulfenamide and N-oxydiethylene-2-benzothiazolylsulfenamide; aldehyde-amine accelerators such as n-butylaldehyde-aniline condensation products and butyraldehyde-monobutylamine condensation products; aldehyde-ammonia accelerators such as hexamethylenetetramine; and thiourea accelerators such as thiocarbanilide. When these vulcanization accelerators are used, one type may be used alone, or two or more types may be used in combination.

[0107] Examples of the vulcanization aid include metal oxides such as zinc oxide (zinc white) and magnesium oxide; metal hydroxides such as potassium hydroxide; metal carbonates such as zinc carbonate and basic zinc carbonate; fatty acids such as stearic acid and oleic acid; aliphatic metal salts such as zinc stearate and magnesium stearate; amines such as n-butylamine and dicyclohexylamine; ethylene dimethacrylate, diallyl phthalate, N,Nm-phenylenedimaleimide, triallyl isocyanurate, trimethylolpropane trimethacrylate, etc. When these vulcanization aids are blended, one type may be used alone, or two or more types may be used in combination.

[0108] Furthermore, the rubber composition according to the present invention may contain one or more of various additives used in the rubber industry, such as antioxidants, vulcanization retarders, peptizers, process oils, plasticizers, etc., as needed.

[0109] Additionally, the present invention provides a molded rubber article produced from the rubber composition.

[0110] The rubber molded product according to an embodiment of the present invention may be a tire. For example, the rubber molded product may be a tire tread. The tire tread is manufactured into a tire by selecting an appropriate blending ratio of raw materials in consideration of the tire application and physical properties, and using a known method.

[0111] According to one embodiment, the rubber composition according to the present invention may be prepared by kneading the above-mentioned components using a kneading machine such as a plastomill, a Banbury mixer, a roll, an internal mixer, etc. Specifically, it is preferable to knead the above-mentioned components except for the crosslinking agent and the vulcanization accelerator, and then add the crosslinking agent and the vulcanization accelerator to the resulting kneaded mixture, followed by further kneading.

[0112] The rubber composition produced by the above-mentioned method can be used as a material for forming the tread portion (and the cap portion including the tread portion) that comes into contact with the road surface. The production method involves extruding the rubber composition according to the tire shape (specifically, the tread shape) into which it must be formed, and molding it in a tire building machine using a conventional method to produce a tire green molded body. This tire green molded body is then heated and pressurized in, for example, a vulcanizer to produce a tire tread, and the desired tire can be manufactured by assembling this tire tread with other components.

[0113] The tires manufactured in this way have excellent mechanical properties (hardness, tensile strength, modulus, etc.), chip break resistance, and adhesion, which are essential for tires. In particular, they have high grip (wet / dry), excellent driving stability and braking performance, and low rolling resistance, which can realize low fuel consumption.

[0114] Therefore, the rubber composition of the present invention is suitable as a rubber composition for obtaining treads of tires such as fuel-efficient tires and high-performance tires.

[0115] The present invention will be described in more detail below through examples, etc. However, the following examples should not be construed as narrowing or limiting the scope and content of the present invention. Furthermore, based on the disclosure of the present invention including the following examples, it is clear that a person skilled in the art can easily practice the present invention, even though no specific experimental results are presented, and it goes without saying that such variations and modifications fall within the scope of the claims.

[0116] Furthermore, the experimental results presented below are only representative experimental results of the above-mentioned Examples and Comparative Examples, and the respective effects of various embodiments of the present invention that are not explicitly presented below will be specifically described in the relevant sections.

[0117] [Example] Example 1: Production of resin composition To 12.52 parts by weight of purified C9 fraction (YNCC), 20.0 parts by weight of viscosity modifier LP-A180 (Kolon Industries), 1.34 parts by weight of molecular weight modifier n-dodecyl mercaptan, 45.61 parts by weight of styrene monomer, and 20.52 parts by weight of xylene solvent were added, followed by the addition of 30.15 parts by weight of polymerization catalyst BF, and the polymerization reaction was carried out for 2.5 hours at 150°C. After the polymerization was completed, the polymer was degassed to remove unreacted reactants, producing a resin composition.

[0118] <Examples 2 and 3, Comparative Examples 1 and 2: Production of Resin Compositions> A resin composition was prepared in the same manner as in Example 1, except that the contents of the purified C9 fraction, viscosity modifier, molecular weight modifier, styrene monomer, and xylene solvent were adjusted as shown in Table 1 below.

[0119] [Table 1]

[0120] <Evaluation example 1: Viscosity measurement> A Brookfield viscometer was used. Spindle No. 27 was used, and 10.5 g samples of the resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were placed in the chamber. After a stabilization time of 30 minutes at 25°C, the RPM value of the stirring shaft was adjusted, and the viscosity values ​​at 50% torque were recorded in Table 2 below.

[0121] <Evaluation example 2: Gardner color scale measurement> The color of the resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was measured according to ASTM D1544. Specifically, the resin compositions were placed in a rectangular quartz cell (20 mm wide, 40 mm long, and 10 mm long). The cell was then attached to a PFX195 colorimeter, which was then operated to measure the Gardner color scale, which was recorded in Table 2 below.

[0122] <Evaluation Example 3: Molecular Weight Evaluation> The polystyrene-equivalent weight-average molecular weight (Mw), number-average molecular weight (Mn), Z-average molecular weight (Mz), and polydispersity (MWD) of the resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were determined by gel permeation chromatography (GPC; size exclusion chromatography (SEC)) (Model HP-1100; product of Hewlett-Packard Co.). The polymers to be measured were dissolved in tetrahydrofuran to a concentration of 4,000 ppm, and 100 μL was injected into the GPC. The mobile phase for GPC was tetrahydrofuran, with a flow rate of 1.0 mL / min. Analysis was performed at 30 °C. Three PIgel (Agilent Technologies) columns (1,000 + 500 + 100 Å) were connected in series. An RI detector (HP-1047A; product of Hewlett-Packard Co.) was used, and measurements were performed at 30 °C. The results are shown in Table 2 below.

[0123] <Evaluation Example 4: Aromaticity Evaluation> The aromaticity of the resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was confirmed by NMR analysis, and the results are shown in Table 2 below.

[0124] [Table 2]

[0125] As can be seen from Table 2, the resin compositions of Examples 1 to 3, which were synthesized using pure styrene monomer as a polymerization component and had a Gardner color scale of 10 or less, were found to satisfy an appropriate viscosity range compared to the resin compositions of Comparative Examples 1 and 2.

Claims

1. The modified petroleum resin has a structure in which a molecular weight regulator is bonded to at least one of both ends of an at least partially hydrogenated or non-hydrogenated petroleum resin, The modified petroleum resin contains at least one unit structure derived from a styrene monomer, The Gardner color scale is 10 or less, The weight average molecular weight (Mw) is 400 to 570, The resin composition, wherein the unit structure derived from the styrene monomer is contained in an amount of more than 0 to less than 100 parts by weight per 100 parts by weight of the modified petroleum resin.

2. The modified petroleum resin is C ９ The resin composition according to claim 1, comprising at least one unit structure derived from a mixed fraction.

3. Said C ９ The resin composition according to claim 2, wherein the unit structure derived from the mixed fraction includes vinyltoluene, α-methylstyrene, styrene, dicyclopentadiene, indene, trans-beta-methylstyrene, and methylindene.

4. The resin composition according to claim 1 , wherein the modified petroleum resin has a structure in which a molecular weight modifier is bonded to both ends of the modified petroleum resin.

5. The resin composition comprises The number average molecular weight (Mn) is 200 to 400; Z-average molecular weight (Mz) is 650 to 4,000; a viscosity measured at 25°C of 5,000 to 50,000 cps; 2. The resin composition according to claim 1, which has a glass transition temperature of −40 to −25° C.

6. The resin composition according to claim 1 , wherein the molecular weight regulator comprises a mercaptan compound containing one or more thiol groups.

7. The resin composition according to claim 6, wherein the mercaptan compound is selected from the group consisting of ethyl mercaptan, butyl mercaptan, hexyl mercaptan, octyl mercaptan, dodecyl mercaptan; phenyl mercaptan, benzyl mercaptan; mercaptoethanol, thiol glycolic acid, mercaptopropionic acid; pentaerythritol tetrakis(3-mercapto)propionate; and any mixture thereof.

8. The resin composition according to claim 1 , further comprising a viscosity modifier.

9. The resin composition according to claim 8, wherein the viscosity modifier comprises a low-viscosity liquid resin having a viscosity of 20 to 500 cps at 25°C.

10. The low viscosity liquid resin is hydrogenated dicyclopentadiene (DCPD)-C ９ 10. The resin composition of claim 9, selected from the group consisting of copolymer resins, hydrogenated dicyclopentadiene (DCPD), and mixtures thereof.

11. the molecular weight modifier is contained in an amount of more than 0 and not more than 15 parts by weight per 100 parts by weight of the total resin composition; The resin composition according to claim 8, wherein the viscosity modifier is contained in an amount of more than 0 and not more than 40 parts by weight per 100 parts by weight of the resin composition.

12. The resin composition comprises a viscosity measured at 25°C of 5,000 to 17,000 cps; 2. The resin composition of claim 1, wherein the aromaticity is from 25% to 70%.

13. C ５ Monomer, C ５ mixed fraction, C ９ Monomer, C ９ A method for producing a resin composition, comprising: adding a polymerization catalyst and / or heat to a solution containing a mixed fraction, one or more of a cyclic diolefin monomer and a linear olefin monomer, and a molecular weight modifier to carry out a polymerization reaction, thereby obtaining a polymerization reaction product; The polymerization reaction product contains at least one unit structure derived from a styrene monomer, The resin composition has a Gardner color scale of 10 or less, the solution further comprises styrene monomer and xylene solvent; The styrene monomer and the xylene solvent are added to the solution in a ratio of 4:1 to 1:1 by weight.

14. The solution is C ９ The C ９ The method for producing a resin composition according to claim 13, wherein the mixed fraction contains vinyltoluene, α-methylstyrene, styrene, dicyclopentadiene, indene, and methylindene.

15. The method for producing a resin composition according to claim 13, wherein the molecular weight regulator comprises a mercaptan compound containing at least one thiol group.

16. The method for producing a resin composition according to claim 13 , wherein the solution further contains a viscosity modifier.

17. The method for producing a resin composition according to claim 16, wherein the viscosity modifier comprises a low-viscosity liquid resin having a viscosity of 20 to 500 cps at 25°C.

18. the molecular weight modifier is contained in an amount of more than 0 and not more than 15 parts by weight per 100 parts by weight of the total resin composition; The method for producing a resin composition according to claim 16, wherein the viscosity modifier is contained in an amount of more than 0 to 40 parts by weight per 100 parts by weight of the total resin composition.

19. The polymerization catalyst is AlCl ３ , B.F. ３ , SnCl ４ , TiCl ４ , AgClO ４ , I ２ 14. The method for producing a resin composition according to claim 13, wherein the Lewis acid catalyst is selected from the group consisting of:

20. The method for producing a resin composition according to claim 13, wherein the application of heat is carried out by raising the temperature to 100°C to 300°C.

21. the polymerization reaction product comprises a mixture of a modified petroleum resin and a viscosity modifier; The modified petroleum resin is converted into the above-mentioned C by a polymerization reaction. ５ Monomer, C ５ mixed fraction, C ９ Monomer, C ９ 17. The method for producing a resin composition according to claim 16, wherein the resin composition has a structure in which the molecular weight regulator is bonded to at least one of both ends of a petroleum resin obtained by polymerizing one or more of a mixed fraction, a cyclic diolefin monomer, and a linear olefin monomer, and which is at least partially hydrogenated or non-hydrogenated.

22. A coating composition comprising the resin composition according to any one of claims 1 to 12.

23. A paint composition comprising the coating composition of claim 22.

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