Resin composition, method for producing the same, 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 adjuster is combined to at least one of both ends of at least partially hydrogenated or non-hydrogenated petroleum resin, wherein the modified petroleum resin includes at least one unit structure from a styrene monomer, wherein the resin composition has a Gardner color of 10 or less.

Description

TECHNICAL FIELD

[0001] The present invention relates to a resin composition, a method of preparing the resin composition, and a coating composition and a paint composition comprising the resin composition. BACKGROUND

[0002] A paint or coating material is manufactured by mixing main materials such as a resin, a curing agent, a solvent, a pigment, and other additives. A commonly used resin for a paint can be a polyester resin, an epoxy resin, or an acrylic resin, but an appropriate resin can be selected according to the purpose of use and the method of use.

[0003] A paint can be used in various fields, for example, wall painting, traffic line engineering, ship coating, coating of metal aggregates, etc. According to the application field, the paint is required to have a temperature change during the coating process and weather resistance after the coating. Specifically, in the case of a paint for a ship, as inorganic particles, for example, talc and ceramic particles are included as additives, the viscosity of the paint increases, and thus the flexibility of the paint decreases, which causes the coating film to be cracked or separated after the coating. In order to solve this problem, various diluents have been studied, but there is still a need for a diluent capable of sufficiently reducing the viscosity of the paint and sufficiently improving the adhesion.

[0004] In addition, since the low viscosity resin developed recently as a diluent has a color, there is still a problem that a color change occurs due to the resin during the manufacturing process of the paint.

[0005] Therefore, there is still a need for a substantially transparent low viscosity resin which not only imparts a low viscosity to a paint, but also has an improved color which does not cause a color change. SUMMARY

[0006] TECHNICAL PROBLEM

[0007] An object of the present invention is to provide a resin composition having both a low viscosity and a Gardner color of 10 or less, and a paint and a rubber composition for a tire comprising the same.

[0008] TECHNICAL SOLUTION

[0009] According to one aspect of the embodiments, there is provided a resin composition comprising a modified petroleum resin having a structure in which a molecular weight adjusting agent is combined to at least one of both ends of at least partially hydrogenated or non-hydrogenated petroleum resin, wherein the modified petroleum resin includes at least one unit structure from a styrene monomer,

[0010] wherein the resin composition has a Gardner color of 10 or less.

[0011] According to another aspect of the embodiments, there is provided a coating material comprising the resin composition.

[0012] According to another aspect of the embodiments, there is provided a paint comprising the coating material.

[0013] According to another aspect of the embodiments, there is provided a method of preparing a resin composition, the method comprising: performing polymerization by adding a polymerization catalyst and / or heating to a solution comprising at least one selected from the group consisting of a C5 monomer, a C5 mixed oil fraction, a C9 monomer, a C9 mixed oil fraction, a cyclic diene monomer, and a straight-chain olefin monomer; and a molecular weight modifier, to obtain a polymerization product,

[0014] wherein the resin composition has a Gardner color of 10 or less.

[0015] Advantages

[0016] When the coating material according to the present application comprises a resin composition having a Gardner color of 10 or less and having a low viscosity, the coating material can provide a low viscosity to a paint and improve color, and has advantages of tire braking, fuel economy, and reduced wear due to excellent mixability with rubber. DETAILED DESCRIPTION

[0017] Hereinafter, various aspects and various embodiments of the present application will be described in further detail.

[0018] As used herein, the term "petroleum resin" includes a polymer prepared by polymerizing at least one selected from a C5 monomer, a C5 mixed oil fraction, a C9 monomer, a C9 mixed oil fraction, a cyclic diene monomer, and a linear olefin monomer. For example, the petroleum resin includes a homopolymer or a copolymer. Examples of the homopolymer of the petroleum resin can include a polymer of a C5 monomer, a polymer of a C5 mixed oil fraction, a polymer of a C9 monomer, a polymer of a C9 mixed oil fraction, a polymer of a cyclic diene monomer, and a polymer of a linear olefin monomer. Examples of the copolymer of the petroleum resin can include a copolymer of two different types of C5 monomers, a copolymer of two different types of C9 monomers, a copolymer of two different types of cyclic diene monomers, a copolymer of two different types of linear olefin monomers, a copolymer of a C5 oil fraction and a C5 monomer, a copolymer of a C5 oil fraction and a C9 monomer, a copolymer of a C9 oil fraction and a C5 monomer, a copolymer of a C5 monomer and a C9 monomer, a copolymer of a C9 oil fraction and a C9 monomer, a copolymer of a C5 oil fraction and a linear olefin monomer, a copolymer of a C9 oil fraction and a linear olefin monomer, a copolymer of a C5 oil fraction and a cyclic diene monomer, a copolymer of a C9 oil fraction and a cyclic diene monomer, a copolymer of a C5 monomer and a cyclic diene monomer, a copolymer of a C9 monomer and a linear olefin monomer, and a copolymer of a cyclic diene monomer and a linear olefin monomer.

[0019] As used herein, the term "hydrogenated petroleum resin" can refer to a petroleum resin in which at least a part of an unsaturated moiety such as ethylene is modified to a saturated hydrocarbon by hydrogenation.

[0020] As used herein, the term "C5 (mixed) oil fraction" includes aliphatic C5 and C6, paraffins, olefins, and dienes from cracking of naphtha. For example, the C5 oil fraction can include pentene, isoprene, 2-methyl-2-butene, 2-methyl-2-pentene, cyclopentadiene, and piperylene, but embodiments are not limited thereto, and can include a mixture of at least two selected from C5 monomers. In addition, the C5 oil fraction can be optionally alkylated.

[0021] As used herein, the term "C5 monomer" means any one selected from components included in a C5 (mixed) oil fraction.

[0022] As used herein, the term "C9 (mixed) oil fraction" includes C8, C9, and / or C 10Olefins, as generally understood in the art to which the present invention pertains, as constituents from petroleum processing, e.g., cracking, and can include, for example, vinyltoluene, alpha-methylstyrene, styrene, dicyclopentadiene, indene, trans-beta-methylstyrene, and methylinde, but embodiments are not limited thereto, and the (mixed) oil fraction includes all mixtures of at least two selected from C9 monomers. Further, the C9 oil fraction can optionally be alkylated. For example, the C9 oil fraction in the present invention can include vinyltoluene, indene, styrene, dicyclopentadiene, and alkylated derivatives of these components, such as alpha-methylstyrene, methylinde, etc.

[0023] As used herein, the term "C9 monomer" means any one selected from components included in a C9 oil fraction.

[0024] As used herein, the term "olefin" includes unsaturated compounds including at least one olefinic unsaturation (C=C) bond. For example, the olefin can include linear olefins, cyclic olefins, or alpha-olefins, but embodiments are not limited thereto.

[0025] As used herein, the term "cyclic diene" includes cyclic unsaturated compounds including two C=C bonds. For example, the cyclic diene can include, but is not limited to, dicyclopentadiene, tricyclopentadiene, etc.

[0026] One aspect of the present invention relates to a method of preparing a resin composition, the method including: performing polymerization by adding a polymerization catalyst and / or heating to a solution including at least one selected from C5 monomers, C5 mixed oil fractions, C9 monomers, C9 mixed oil fractions, cyclic diene monomers, and linear olefin monomers; and a molecular weight modifier, to obtain a polymerization product, wherein the modified petroleum resin includes at least one unit structure from a styrene monomer, wherein the resin composition has a Gardner color of 10 or less.

[0027] According to one embodiment, the solution can further include a viscosity modifier. In this aspect, the viscosity of the polymerization product can be easily controlled.

[0028] Since the viscosity modifier does not participate in the formation of the structure of the polymer as a product, but rather functions as a modifier to control the viscosity of the reactants and the product, the polymerization product according to the present invention prepared by performing polymerization by adding a polymerization catalyst and / or heating to a solution including at least one selected from C5 monomers, C5 mixed oil fractions, C9 monomers, C9 mixed oil fractions, cyclic diene monomers, and linear olefin monomers; a molecular weight modifier; and a viscosity modifier can be a mixture of a modified polymer and a viscosity modifier.

[0029] According to one embodiment, the solution can include styrene monomer and xylene solvent. Here, the styrene monomer refers to pure styrene monomer. The Gardner color of the petroleum resin thus obtained is 10 or less. For example, the Gardner color of the petroleum resin can be in the range of 0 to 10, 1 to 10, 1 to 10, 3 to 10, or 4 to 10.

[0030] According to one embodiment, the method can further include modifying the petroleum resin into a hydrogenated petroleum resin by hydrogenating the petroleum resin in the presence of a catalyst.

[0031] The catalyst used in the hydrogenation can be a hydrogenation catalyst well known in the field of petroleum resins, and examples of the hydrogenation catalyst can be Pd, Ni, Pt, or a mixture thereof.

[0032] According to one embodiment, the xylene solvent can be added to prevent the deterioration of processability due to monomer densification caused by the addition of the styrene monomer. For example, the styrene monomer and the xylene solvent can be added to the solution in a ratio in the range of 4:1 to 1:1 on a weight basis. For example, the styrene monomer and the xylene solvent can be added to the solution in a ratio in the range 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 on a weight basis.

[0033] In addition, the xylene solvent is added to control the monomer concentration in the polymerization system increased by the addition of the pure styrene monomer, and the heat generation caused by the increase in the monomer concentration during the polymerization process can be prevented by adding the xylene solvent.

[0034] According to one embodiment, the amount of the molecular weight modifier can be in the range of greater than 0 parts by weight and equal to or less than 15 parts by weight based on 100 parts by weight of the total weight of the resin composition, and the amount of the viscosity modifier can be in the range of greater than 0 parts by weight and equal to or less than 40 parts by weight based on 100 parts by weight of the total weight of the resin composition.

[0035] For example, the amount of the molecular weight modifier can be in the range of 1 part by weight to 10 parts by weight, 1 part by weight to 5 parts by weight, 1 part by weight to 2.5 parts by weight, or 1 part by weight to 1.4 parts by weight.

[0036] For example, the amount of the viscosity modifier can be in the range of 10 parts by weight to 30 parts by weight or 15 parts by weight to 25 parts by weight.

[0037] When the amounts of the molecular weight adjusting agent and the viscosity adjusting agent are within these ranges, a low viscosity petroleum resin having good mixing properties with raw coating materials can be prepared. When the molecular weight adjusting agent is not included, a petroleum resin having a high molecular weight and a high viscosity is obtained, and when the amount of the molecular weight adjusting agent is greater than 15 parts by weight, the viscosity is excessively reduced or the degree of polymerization is reduced, which causes deterioration of the coating properties of the final product (e.g., a coating). In addition, the viscosity adjusting agent is added to reduce the viscosity of the modified petroleum resin, which can be added as needed, but when the amount of the viscosity adjusting agent is greater than 40 parts by weight, the viscosity is excessively reduced, which causes deterioration of the coating properties of the final product (e.g., a coating). Therefore, the molecular weight adjusting agent and the viscosity adjusting agent need to be mixed in an appropriate ratio.

[0038] According to one embodiment, the molecular weight adjusting agent that can be used in the present application can be a chain transfer agent, and examples of the chain transfer agent can include a mercaptan or a halogenated carbon such as carbon tetrachloride.

[0039] For example, the molecular weight adjusting agent can be a mercaptan, i.e., an organic mercaptan-based molecular weight adjusting agent including at least one mercapto group (-SH), and examples of the organic mercaptan-based molecular weight adjusting agent can include an aliphatic mercaptan, an alicyclic mercaptan, or an aromatic mercaptan.

[0040] The mercaptan can include 1 to 4 mercapto groups per molecule, and can include 1 to 20 carbons, preferably 1 to 15 carbons, per mercapto group.

[0041] In addition, the mercaptan can include other substituents in addition to the hydrocarbon group and the mercapto group, and examples of the substituents can include a hydroxyl group, a carboxylic acid group, an ether group, an ester group, a sulfide group, an amino group, and an amide group.

[0042] The mercaptan used as the molecular weight adjusting agent in the present application is not particularly limited as long as it is an organic compound having a mercapto group, and specifically, can be: an alkyl mercaptan such as ethyl mercaptan, butyl mercaptan, hexyl mercaptan, octyl mercaptan, or dodecyl mercaptan; a mercaptan phenol such as phenyl mercaptan or benzyl mercaptan; a mercaptan including a hydroxyl group or a carboxylic acid group such as 2-mercaptoethanol, mercaptoacetic acid, or 3-mercaptopropionic acid; or a mercaptan having two or more functional groups such as pentaerythritol tetra(3-mercaptopropionate); or a mixture selected from at least two or more of them.

[0043] Examples of such thiols 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'-dithiodiethylether, 2,2'-dithiodipropylether, 2,2'-dithiodiisopropylether, 3,3'-dithiodipropylether, 2,2'-dithiodiethylsulfide, 3,3'-dithiodipropylsulfide, bis(β-mercaptoethoxy)methane, bis(β-mercaptoethylthio)methane, trimethylolpropane tris-mercaptopropionate, and pentaerythritol tetra-mercaptopropionate.

[0044] According to one embodiment, examples of the molecular weight regulator of the present application can include: ethyl mercaptan, butyl mercaptan, hexyl mercaptan, octyl mercaptan, dodecyl mercaptan; phenyl mercaptan, benzyl mercaptan; mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid; and pentaerythritol tetra(3-mercapto)propionate.

[0045] For example, when n-dodecyl mercaptan of Formula 1, 2-mercaptoethanol of Formula 2, or a mixture thereof is used as the molecular weight regulator in the present application, the effect of the molecular weight regulator can be maximized.

[0046] [Formula 1]

[0047]

[0048] [Formula 2]

[0049]

[0050] According to one embodiment, a low viscosity liquid resin having a viscosity (at 25°C) in the range of 20 cps to 500 cps can be used as the viscosity regulator, and any liquid resin having a viscosity in this range can be used as the viscosity regulator for the resin composition according to one embodiment of the present application, without particular limitation.

[0051] For example, the low viscosity liquid resin can be selected from the group consisting of hydrogenated dicyclopentadiene (DCPD)-C9 copolymer resins, hydrogenated DCPD resins, and mixtures thereof.

[0052] Here, the hydrogenated DCPD-C9 copolymer resin refers to a white thermoplastic resin obtained by polymerization and hydrogenation of DCPD, and as the hydrogenated DCPD-C9 copolymer resin, commercial resins such as Resin.

[0053] For example, when a hydrogenated DCPD-C9 copolymer resin having the following structure is used as the viscosity regulator, the viscosity control effect and improvement in air permeation resistance can be maximized.

[0054] [Formula 3]

[0055]

[0056] According to one embodiment, one selected from a Lewis acid catalyst, a hydrogen halide acid, AlCl3, BF3, and a mixture of at least two thereof can be used as a polymerization catalyst.

[0057] Preferably, a Lewis acid catalyst selected from AlCl3, BF3, SnCl4, TiCl4, AgClO4, I2, and a mixture of at least two thereof can be used as a polymerization catalyst.

[0058] According to one embodiment, the heating can be performed by raising the temperature to 100°C to 300°C.

[0059] One aspect of the present application relates to a resin composition comprising: a modified petroleum resin having a structure in which a molecular weight adjusting agent is combined to at least one terminal of at least partially hydrogenated or non-hydrogenated petroleum resin; and a viscosity adjusting agent, wherein the modified petroleum resin includes at least one unit structure from a styrene monomer, and wherein the resin composition has a Gardner color of 10 or less.

[0060] According to one embodiment, the petroleum resin or hydrogenated petroleum resin can include a styrene monomer as a polymerization raw material.

[0061] Here, the styrene monomer refers to a pure styrene monomer, and when the pure styrene monomer is included as a polymerization raw material, the petroleum resin can have a color improvement effect. For example, the Gardner color of the modified petroleum resin can be in a range of greater than 0 to 10 or less or 1 or more to 10 or less. When the Gardner color of the resin composition is in this range, not only can the color change of a paint mixed with the resin composition be prevented, but also the amount of a pigment added for whiteness can be reduced, and thus the resin composition is economically preferable.

[0062] According to one embodiment, the amount of the unit structure from the styrene monomer can be in a range of greater than 0 parts by weight to less than 100 parts by weight, based on 100 parts by weight of the modified petroleum resin.

[0063] For example, the amount of the unit structure from the styrene monomer can be in a range of 13 parts by weight to 95 parts by weight, 15 parts by weight to 90 parts by weight, 20 parts by weight to 85 parts by weight, or 27 parts by weight to 80 parts by weight, based on 100 parts by weight of the modified petroleum resin, but embodiments are not limited thereto.

[0064] According to one embodiment, the modified petroleum resin is prepared by polymerizing at least one selected from C5 monomers, C5 mixed oil fractions, C9 monomers, C9 mixed oil fractions, cyclic diene monomers, and linear olefin monomers, and modifying the at least partially hydrogenated or non-hydrogenated petroleum resin using a molecular weight modifier. When the petroleum resin includes a unit structure from a styrene monomer, a petroleum resin having a lower Gardner color, for example, a Gardner color of 10 or less, than a conventional petroleum resin that does not include a unit structure from a styrene monomer can be obtained.

[0065] According to one embodiment, the modified petroleum resin has a structure in which at least one selected from C5 monomers, C5 mixed oil fractions, C9 monomers, C9 mixed oil fractions, cyclic diene monomers, and linear olefin monomers is polymerized by addition polymerization or chain polymerization, and a structure in which a molecular weight modifier is bound to at least one of both ends of the at least partially hydrogenated or non-hydrogenated petroleum resin.

[0066] For example, the petroleum resin can include at least one unit structure from a C9 mixed oil fraction or a repeating unit from a C9 mixed oil fraction.

[0067] According to one embodiment, examples of the unit structure from a C9 mixed oil fraction can include vinyltoluene, α-methylstyrene, styrene, dicyclopentadiene, indene, and methylinde.

[0068] According to one embodiment, the petroleum resin can include a structure in which a repeating unit represented by Formula 4a, Formula 4b, or Formula 4c is bound. Here, although not shown in the structural formula, a repeating unit from a styrene monomer in the petroleum resin can account for 60% to 95%, for example, 75% to 95%, of repeating units in the petroleum resin.

[0069] According to one embodiment, the petroleum resin includes a structure in which a repeating unit of Formula 4a is bound. For example, the petroleum resin can include the following structure formed when a monomer (such as styrene, α-methylstyrene, vinyltoluene, indene, methylinde, dicyclopentadiene, and α-methylstyrene or methylinde) contained in a C9 mixed oil fraction or an alkylated derivative monomer of these components participates in polymerization.

[0070] [Formula 4a]

[0071]

[0072] Formula 4a is only one example, and thus, the petroleum resin can include repeating units from other C5 monomers, C9 monomers, cyclic diene monomers, and linear olefin monomers not shown in Formula 4a.

[0073] For example, the petroleum resin may be a polymer including the structure described above. This polymer refers to a random polymer, but is not limited thereto, and may include block copolymers or alternating copolymers.

[0074] Although not shown in the structural formula, the petroleum resin may include at least one of the repeating units shown in formula 4a that has been hydrogenated.

[0075] According to another embodiment, the petroleum resin may include a structure incorporating repeating units as shown below. For example, the petroleum resin has a structure in which one of its two ends has a double bond, and Formula 4b shows a structure in which both ends have double bonds as an example.

[0076] [Formula 4b]

[0077]

[0078] In this respect, the double bond at at least one end is bonded to a molecular weight regulator, thereby forming a petroleum resin (e.g., a polymer of a C9 monomer) modified with the molecular weight regulator. The molecular weight regulator may be bonded to both ends, or to either end, as shown in Formula 4c as an example.

[0079] Although not shown in the structural formula, the petroleum resin may include a structure in which at least one of the repeating units shown in Formula 4b or Formula 4c is hydrogenated.

[0080] [Formula 4c]

[0081]

[0082] According to one embodiment, the number-average molecular weight (M0) of the resin composition is... n The number-average molecular weight (Mw) can be in the range of 200 to 400, the weight-average molecular weight (Mw) can be in the range of 400 to 700, the z-average molecular weight (Mz) can be in the range of 650 to 5000, and the dispersibility can be in the range of 1 to 3. Preferably, the number-average molecular weight (Mw) of the resin composition is in the range of 200 to 400, the weight-average molecular weight (Mw) can be in the range of 400 to 700, the z-average molecular weight (Mz) can be in the range of 650 to 5000, and the dispersibility can be in the range of 1 to 3. n The molecular weight (Mw) can be in the range of 200 to 350, the weight-average molecular weight (Mw) can be in the range of 400 to 570, the Z-average molecular weight (Mz) can be in the range of 650 to 5000, and the dispersion can be in the range of 1.5 to 3.

[0083] When the number average molecular weight is lower than 200, the mixing efficiency is reduced, and when the number average molecular weight is higher than 400, the mixing processability is reduced. In addition, since the molecular weight is in such a low range, the processability of the resin composition can be excellent, and thus the resin composition can be applied to a low viscosity coating, so that an excellent coating film can be coated.

[0084] According to one embodiment, the viscosity of the resin composition at 25°C is in the range of 5,000 cps to 50,000 cps, and the glass transition temperature is in the range of -40°C to -25°C.

[0085] When the glass transition temperature is lower than -40°C, not only the volatility of the resin composition is high, but also the coating performance of the resin composition is reduced due to low viscosity. When the glass transition temperature is higher than -25°C, the viscosity of the coating prepared using the resin composition is not low enough, so that the processability is reduced, and since the sufficient flexibility of the coating cannot be ensured, cracks can occur in the coated material.

[0086] According to one embodiment, the resin composition can further include a viscosity modifier.

[0087] According to one embodiment, the amount of the viscosity modifier can be in the range of greater than 0 parts by weight and equal to or less than 40 parts by weight, based on 100 parts by weight of the resin composition.

[0088] As described above, when the modified petroleum resin according to one embodiment of the present application further includes a viscosity modifier, the modified petroleum resin can be obtained by adding a polymerization catalyst and / or heating to perform polymerization to a solution including at least one selected from a C5 monomer, a C5 mixed oil fraction, a C9 monomer, a C9 mixed oil fraction, a cyclic diene monomer, and a linear olefin monomer; a molecular weight modifier; and a viscosity modifier, wherein the viscosity modifier does not participate in the formation of the structure of the modified petroleum resin as a product, but controls the viscosity of the reactants and the product, and thus the polymerization product can be a mixture of the modified polymer and the viscosity modifier.

[0089] Descriptions of the C5 monomer, the C5 mixed oil fraction, the C9 monomer, the C9 mixed oil fraction, the cyclic diene monomer, the linear olefin monomer, and the pure styrene monomer can refer to those described above, and each embodiment of the molecular weight modifier or the viscosity modifier is the same as described above.

[0090] According to one embodiment, the viscosity of the resin composition measured at a temperature of 25°C can be in the range of 5,000 cps to 50,000 cps, for example, 5,000 cps to 17,000 cps or 5,000 cps to 15,000 cps.

[0091] The aromaticity of the resin composition can be in the range of 25% to 70%, for example, 30% to 60% or 35% to 50%.

[0092] When the aromaticity of the resin composition is in the range, sufficient compatibility of the resin composition with the coating material is obtained, whereby a coated material having excellent processability and durability can be formed.

[0093] One aspect of the present application relates to a coating composition comprising the resin composition.

[0094] According to one embodiment, the coating composition can comprise a base resin, the resin composition, a curing agent, a curing accelerator, a pigment, an additive, and a solvent.

[0095] According to the use of the low viscosity resin composition, the coating composition can not comprise a plasticizer.

[0096] According to one embodiment, the base resin can include an epoxy-based resin.

[0097] According to one embodiment, the curing agent can include a heat curing agent, a light curing agent, or an ultraviolet curing agent well known in the art, and can be appropriately selected therefrom according to the use.

[0098] According to one embodiment, a curing accelerator is added to control the curing rate of the curing agent, and the curing accelerator includes a sulfonic acid curing catalyst or a urethane curing catalyst, wherein the curing accelerator can be appropriately selected from the curing accelerators well known in the art as needed.

[0099] According to one embodiment, the pigment is added to provide color or increase whiteness to the coating composition, and the pigment can include an inorganic pigment such as titanium dioxide, but the embodiment is not limited thereto, and any pigment well known in the art can be appropriately selected and used. For example, the resin composition according to one embodiment of the present application can reduce the amount of the pigment added, thereby improving economic efficiency, since the Gardner color is 10 or less, for example, in the range of 1 or more to 10 or less.

[0100] According to one embodiment, the additive can include all components that can be mixed to the coating material, in addition to the curing agent, the curing accelerator, the pigment, and the solvent. For example, the additive can include a surface modifier, a light stabilizer, a weatherability additive, a preservative, an appearance modifier, a defoaming agent, a leveling agent, or a combination thereof. These additives can be appropriately selected from the materials commonly used in the art.

[0101] According to one embodiment, the solvent can be selected from solvents having good mixability with coating raw materials, for example, an organic solvent can be used.

[0102] The raw materials described above mixed with the coating composition can be mixed appropriately with reference to a conventional composition in consideration of the purpose of use of a person having ordinary skill in the art or the desired viscosity and color.

[0103] One aspect of the present application relates to a rubber composition comprising: raw rubber; and the resin composition according to one or more embodiments of the present application.

[0104] According to one embodiment, the rubber composition can further comprise at least one selected from the group consisting of raw rubber, a reinforcing agent, a silane coupling agent, a vulcanizing agent, and a vulcanization accelerator, in addition to the modified petroleum resin and the viscosity modifier.

[0105] The raw rubber can include natural rubber having an olefinic double bond, synthetic rubber having an olefinic double bond, or a combination thereof.

[0106] The raw rubber is not particularly limited as long as it is any rubber having an olefinic double bond (carbon-carbon double bond), and natural rubber, synthetic rubber, or a mixture thereof can be used.

[0107] For example, the raw rubber can 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.

[0108] The reinforcing agent can include carbon black and silica.

[0109] When the rubber composition comprises carbon black, effects such as improvement of wear resistance, improvement of rotation resistance, and prevention of cracks or cracks due to ultraviolet rays (prevention of ultraviolet degradation) can be obtained. The carbon black used in the present application is not particularly limited, and any material generally used as carbon black in the art can be used.

[0110] According to one embodiment, examples of the carbon black can include furnace black, acetylene black, thermal black, channel black, graphite, or a combination thereof.

[0111] For example, the physical properties of the carbon black such as particle diameter, pore volume, or specific surface area are not particularly limited, and various carbon blacks used in the conventional rubber industry such as SAF, ISAF, HAF, FEF, GPF, SRF (all of which are abbreviations of carbon black classified in the U.S. such as ASTM standard D-1765-82a) can be used.

[0112] In addition, silica used as a reinforcing agent for rubber can be used without particular limitation, and examples of the silica can include dry white carbon, wet white carbon, synthetic silicate white carbon, colloidal silica, and precipitated silica. Although the specific surface area of the silica is not particularly limited, the specific surface area can generally be in the range of 40 m 2 / g to 600 m 2 / g, for example, 70 m 2 / g to 300 m 2 / g, and the primary particle diameter of the silica can be in the range of 10 nm to 1000 nm. Examples of the silica can be used alone, or can be used as a combination of at least two selected from among them.

[0113] Examples of the reinforcing agent other than carbon black and silica can include powders of minerals such as clay and talc; carbonates such as magnesium carbonate and calcium carbonate; and alumina hydrate such as aluminum hydroxide.

[0114] According to one embodiment, the silane coupling agent is used for mixing silica, wherein examples of the silane coupling agent can include: vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(β-methoxy-ethoxy)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-triethoxysilyl ethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilyl ethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilyl ethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzoyltetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, or combinations thereof. For example, the silane coupling agent can include bis(3-(triethoxysilyl)propyl)tetrasulfide.

[0115] The crosslinking agent can be any material commonly used in crosslinking of rubber, and can be appropriately selected depending on the rubber component and the isobutylene-based polymer.

[0116] According to one embodiment, examples of the crosslinking agent can include: sulfur crosslinking agents such as sulfur, morpholine disulfide, and alkylphenol disulfide; and organic peroxide crosslinking agents such as cyclohexanone peroxide, methyl acetoacetate peroxide, t-butyl peroxyisobutyrate, t-butyl peroxybenzoate, benzoyl peroxide, lauryl peroxide, dicumyl peroxide, di-t-butyl peroxide, and 1,3-bis(t-butylperoxyisopropyl)benzene.

[0117] The rubber composition for a tire tread according to the present application can include a vulcanization accelerator and a vulcanizing agent.

[0118] According to one embodiment, the vulcanization accelerators and vulcanizing agents are not particularly limited, and can be appropriately selected and used depending on the rubber component, isobutylene polymer, and crosslinking agent included in the rubber composition. Here, "vulcanization" means crosslinking by at least one sulfur atom.

[0119] Examples of the vulcanization accelerator can include: thiuram-based 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-benzothiazole sulfenamide and N-oxydiphenylene-2-benzothiazole sulfenamide; aldehyde amine-based accelerators such as n-butyraldehyde-aniline condensate and butyraldehyde-monobutylamine condensate; aldehyde amine-based accelerators such as cyclohexanediamine tetraamine; and thiourea accelerators such as diphenylthiourea. When mixing the vulcanization accelerators, one type of vulcanization accelerator can be used, or at least two selected from the examples of the vulcanization accelerator can be used in combination.

[0120] Examples of the vulcanizing agent can include: metal oxides such as zinc oxide (galvanized) and magnesium oxide; metal hydroxides such as calcium 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; dimethyl vinyl acrylate; diallyl phthalate; N,N-m-phenylenediamine dimaleimide; triallyl isocyanurate; and trimethylolpropane trimethacrylate. When mixing the vulcanizing agents, one type of vulcanizing agent can be used, or at least two selected from the examples of the vulcanizing agent can be used in combination.

[0121] In addition, the rubber composition according to the present application can include various additives used in the field of rubber industry, for example, one or at least two selected from anti-aging agents, vulcanization retardants, peptizers, processing oils, and plasticizers.

[0122] In addition, the present application provides a rubber molded article prepared using the rubber composition.

[0123] The rubber molded article according to one embodiment of the present application can be a tire. For example, the rubber molded article can be a tire tread. The tire tread is prepared into a tire by a known method by selecting an appropriate raw material mixing ratio, considering the use and physical properties of the tire.

[0124] According to one embodiment, the rubber composition according to the present application can be prepared by mixing the above-mentioned respective components using a mixer such as a plastomill, a Banbury mixer, a roll, or a closed mixer. Specifically, the components other than the crosslinking agent and the vulcanization accelerator among the above-mentioned components are preferably mixed, and then the crosslinking agent and the vulcanization accelerator are added to the resulting mixture, followed by further mixing.

[0125] The rubber composition thus prepared using the method can be used as a material constituting a tread portion (and a cap portion including the tread portion) which comes into contact with a road surface. According to the preparation method, the rubber composition is extruded according to the shape of the tire to be formed (particularly, the shape of the tread), and is molded on a tire molding machine by a conventional method, to manufacture an uncrosslinked molded body for a tire. The tire tread is manufactured by, for example, heating and pressing the uncrosslinked molded body for a tire in a vulcanizer, and the desired tire can be manufactured by assembling the resulting tire tread and other components.

[0126] The tire thus manufactured has excellent mechanical properties (hardness, tensile strength, modulus, etc.), chip resistance and cut resistance, and adhesion properties as a tire should have. Specifically, the manufactured tire has high adhesion properties (wet road), and is thus excellent in terms of running stability of a vehicle, traction performance of a brake, and relatively low rolling resistance, thereby achieving low fuel cost of the vehicle.

[0127] Accordingly, the composition for a tire tread of the present application is suitable as a composition for a tread of a tire for obtaining a tire such as a low fuel cost tire and a high performance tire.

[0128] Hereinafter, the present application will be described in further detail with reference to the following examples, which are presented for illustrative purposes only and should not be construed as limiting the scope of the present application. In addition, based on the disclosure of the present application including the following examples, it is obvious to those of ordinary skill in the art that the present application can be easily modified or corrected.

[0129] In addition, the experimental data provided herein are only representative experimental results of the examples and comparative examples, and the effects of respective different embodiments of the present application which are not explicitly provided hereinafter will be described in detail in the corresponding sections.

[0130] [Examples]

[0131] Example 1: Preparation of resin composition

[0132] A resin composition was prepared in the same manner as in Example 1, except that the amounts of the purified C9 oil fraction, the viscosity modifier, the molecular weight modifier, the styrene monomer, and the xylene solvent were controlled to be the amounts shown in Table 1.

[0133] Example 2 and Example 3 and Comparative Example 1 and Comparative Example 2: Preparation of resin composition

[0134] A resin composition was prepared in the same manner as in Example 1, except that the amounts of the purified C9 oil fraction, the viscosity modifier, the molecular weight modifier, the styrene monomer, and the xylene solvent were controlled to be the amounts shown in Table 1.

[0135] [Table 1]

[0136]

[0137] Evaluation Example 1: Viscosity measurement

[0138] A viscometer available from Brookfield was used. A No. 27 spindle was used, and 10.5 g of the resin composition prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was added as a sample in a chamber. After stabilization for 30 minutes at 25°C, the viscosity value at a Torque value of 50% was recorded in Table 1 by controlling the stirring shaft RPM value.

[0139] Evaluation Example 2: Gardner color measurement

[0140] Color measurement was performed on the resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 using ASTM D1544. Specifically, the resin composition was added to a rectangular quartz cell (20 mm in width, 40 mm in length, and 10 mm in path length). The cell was equipped in a PFX195 colorimeter to measure the Gardner color, and the results are shown in Table 2.

[0141] Evaluation Example 3: Molecular weight evaluation

[0142] The weight average molecular weight (Mw), number average molecular weight (Mn), Z average molecular weight (Mz), and dispersity (MWD) of the resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were obtained in terms of polystyrene using a gel permeation chromatograph (model name: HP-1100, available from Hewlett-Packard Co., Ltd.). The polymer to be measured was dissolved in tetrahydrofuran to a concentration of 4000 ppm, and 100 μl of the sample was injected into the GPC. The mobile phase of the GPC was tetrahydrofuran, which was flown at a flow rate of 1.0 mL / minute, and the analysis was performed at 30°C. The chromatographic column was prepared by connecting three PIgel columns manufactured by Agilent in series. A refractive index (RI) detector (HP-1047A available from Hewlett-Packard) was used as the detector measured at 30°C. The results are shown in Table 2.

[0143] Evaluation Example 4: Aromaticity evaluation

[0144] The aromaticity of the resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was confirmed by NMR analysis. The results are shown in Table 2.

[0145] [Table 2]

[0146]

[0147] As shown in the table, it can be confirmed that the resin compositions of Examples 1 to 3, which were synthesized using pure styrene monomer as the polymerization component and had a Gardner color of 10 or less, satisfied the appropriate viscosity range compared to the resin compositions of Comparative Examples 1 and 2.

Claims

1. A resin composition comprising: a modified petroleum resin having a structure in which a molecular weight modifier is bound to at least one of two ends of at least partially hydrogenated or non-hydrogenated petroleum resin, wherein the modified petroleum resin includes at least one unit structure from a styrene monomer, wherein the resin composition has a Gardner color of 10 or less, wherein the resin composition has: a number average molecular weight (Mn) in the range of 200 to 400, a weight average molecular weight (Mw) in the range of 400 to 700, a Z average molecular weight (Mz) in the range of 650 to 5,000, wherein the modified petroleum resin includes at least one unit structure from a C9 mixed oil fraction, wherein the resin composition further comprises a viscosity modifier, wherein the amount of the unit structure from a styrene monomer is in the range of 13 parts by weight to 95 parts by weight, based on 100 parts by weight of the modified petroleum resin, wherein the molecular weight modifier includes a mercaptan compound including at least one mercapto group, wherein the content of the molecular weight modifier is in the range of greater than 0 parts by weight and equal to or less than 15 parts by weight, based on 100 parts by weight of the total weight of the resin composition, wherein the viscosity modifier includes a low viscosity liquid resin selected from a hydrogenated dicyclopentadiene (DCPD)-C9 copolymer resin, a hydrogenated dicyclopentadiene resin, and mixtures thereof, and wherein the content of the viscosity modifier is in the range of greater than 0 parts by weight and equal to or less than 40 parts by weight, based on 100 parts by weight of the total weight of the resin composition.

2. The resin composition according to claim 1, wherein, the unit structure from a C9 mixed oil fraction includes vinyltoluene, α-methylstyrene, styrene, dicyclopentadiene, indene, trans-β-methylstyrene, and methoindene.

3. The resin composition according to claim 1, wherein, the modified petroleum resin has a structure in which a molecular weight modifier is bound to the two ends.

4. The resin composition according to claim 1, wherein, the resin composition has: a viscosity in the range of 5,000 cps to 50,000 cps measured at 25℃, and a glass transition temperature in the range of -40℃ to -25℃.

5. The resin composition according to claim 1, wherein, the mercaptan compound is selected from the group consisting of ethanethiol, butanethiol, hexyl mercaptan, octyl mercaptan, dodecyl mercaptan, phenyl mercaptan, benzyl mercaptan, mercaptoethanol, mercaptoacetic acid, mercaptopropionic acid, pentaerythritol tetra(3-mercapto)propionate, and any mixtures thereof.

6. The resin composition according to claim 1, wherein, the low viscosity liquid resin has a viscosity in the range of 20 cps to 500 cps at 25℃. 7.The resin composition of claim 1, wherein, the resin composition has a viscosity in the range of 5,000 cps to 17,000 cps measured at 25℃, and the resin composition has an aromaticity in the range of 25% to 70%. 8.A method of preparing a resin composition, the method comprising: carrying out polymerization by adding a polymerization catalyst and / or heating to a solution including a C9 mixed oil fraction and at least one selected from a C5 monomer, a C5 mixed oil fraction, a C9 monomer, a cyclic diene monomer, and a linear olefin monomer; and a molecular weight modifier, to obtain a polymerization product, wherein the polymerization product includes at least one unit structure from a styrene monomer, wherein the resin composition has a Gardner color of 10 or less, and wherein the resin composition has: a number average molecular weight (Mn) in the range of 200 to 400, a weight average molecular weight (Mw) in the range of 400 to 700, a Z average molecular weight (Mz) in the range of 650 to 5000, wherein the polymerization product includes a modified petroleum resin and a viscosity modifier, wherein the modified petroleum resin has at least one structure polymerized from a C9 mixed oil fraction, wherein the amount of the unit structure from the styrene monomer is in the range of 13 parts by weight to 95 parts by weight, based on 100 parts by weight of the modified petroleum resin, wherein the molecular weight modifier includes a mercaptan compound including at least one mercapto group, wherein the content of the molecular weight modifier is in the range of greater than 0 parts by weight and equal to or less than 15 parts by weight, based on 100 parts by weight of the total weight of the resin composition, wherein the viscosity modifier includes a low viscosity liquid resin selected from a hydrogenated dicyclopentadiene (DCPD)-C9 copolymer resin, a hydrogenated dicyclopentadiene resin, and mixtures thereof, and wherein the content of the viscosity modifier is in the range of greater than 0 parts by weight and equal to or less than 40 parts by weight, based on 100 parts by weight of the total weight of the resin composition.

9. The method of claim 8, wherein, The solution further includes a styrene monomer and a xylene solvent.

10. The method of claim 9, wherein, The styrene monomer and the xylene solvent are included in the solution in a ratio in the range of 4:1 to 1:1 on a weight basis.

11. The method of claim 8, wherein, The C9 mixed oil fraction includes vinyltoluene, alpha-methylstyrene, styrene, dicyclopentadiene, indene, and methylinde.

12. The method of claim 8, wherein, The low viscosity liquid resin has a viscosity in the range of 20 cps to 500 cps at 25°C.

13. The method of claim 8, wherein, The polymerization catalyst is a Lewis acid catalyst selected from AlCl3, BF3, SnCl4, TiCl4, AgClO4, I2, and mixtures of at least two thereof.

14. The method of claim 8, wherein, The heating is performed by heating the temperature to 100°C to 300°C.

15. The method of claim 8, wherein The modified petroleum resin has at least one polymerization of at least one selected from a C5 monomer, a C5 mixed oil fraction, a C9 monomer, a cyclic diene monomer, and a linear olefin monomer, and the molecular weight modifier is bonded to a structure of at least one of two terminal ends of the at least partially hydrogenated or non-hydrogenated petroleum resin.

16. A coating composition including the resin composition of any one of claims 1 to 7.

17. A coating composition including the coating composition of claim 16.

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