Plasticizers, compositions and tires

Abstract

This invention provides a plasticizer capable of altering tire properties within a temperature range required by the tire, and can also be used to prepare tire compositions, as well as the compositions and tires thereof. This invention relates to plasticizers for use in resins and / or elastomers, the plasticizer comprising groups whose interaction with antifreeze changes with temperature, the lower critical dissolution temperature of which is from -20°C to 20°C.

Description

Technical Field

[0001] This invention relates to plasticizers, compositions, and tires. Background Technology

[0002] Tires with a variety of desirable properties are desired (see, for example, Patent Document 1).

[0003] Reference List

[0004] Patent documents

[0005] Patent document 1: JP2008-214377A Summary of the Invention

[0006] Technical issues

[0007] However, to date, the tire industry has not focused on changing tire performance within the temperature range required by tires, and there is room for improvement in traditional technologies for changing tire performance within this temperature range.

[0008] The present invention aims to solve the above-mentioned problems and provide a plasticizer that can change tire performance within the temperature range required by the tire and can also be used to prepare tire compositions, as well as plasticizer compositions and tires.

[0009] Solution

[0010] The present invention relates to a plasticizer for at least one resin or elastomer, the plasticizer comprising a group whose interaction with an antifreeze agent changes with temperature, the lower critical solution temperature of the group being -20°C to 20°C.

[0011] Beneficial effects of the invention

[0012] The plasticizers of the resins and / or elastomers of the present invention contain a group whose interaction with the antifreeze changes with temperature, and the lower critical dissolution temperature of the group is -20°C to 20°C. Therefore, the plasticizers can modify tire performance within the temperature range required by the tire and can also be used to prepare tire compositions. Detailed Implementation

[0013] (Plasticizer)

[0014] The plasticizer of the present invention is a plasticizer for resins and / or elastomers, the plasticizer containing a group whose interaction with the antifreeze changes with temperature, and the lower critical dissolution temperature of the group being -2°C to 20°C. This plasticizer can modify tire performance within the temperature range required by the tire and can also be used to prepare tire compositions.

[0015] The reasons for this beneficial effect are not entirely clear, but are believed to be as follows.

[0016] Since the plasticizer of the present invention contains groups whose interaction with the antifreeze changes with temperature, it is believed that temperature changes can alter hydrophilicity and thus compatibility with other components in the composition, and therefore tire performance can change in response to temperature changes.

[0017] Furthermore, since the lower critical dissolution temperature of this group is -20°C to 20°C, the plasticizer can modify tire performance within the required temperature range. Specifically, the plasticizer acts as a hydrophobic plasticizer at temperatures above the lower critical dissolution temperature of the group, and as a hydrophilic plasticizer at temperatures below the lower critical dissolution temperature. Therefore, the plasticizer can modify tire performance within this boundary temperature range, thereby enabling the modification of tire performance within the required temperature range (e.g., -40°C to 40°C).

[0018] Furthermore, the lower critical dissolution temperature within the aforementioned range minimizes the impact on the resin and / or elastomer, which are the main chain components of the tire composition. Therefore, plasticizers can be used to prepare tire compositions.

[0019] For example, the plasticizer of the present invention can improve overall performance in terms of fuel economy and wet grip.

[0020] In this document, the term "plasticizer" refers to a material that imparts plasticity to resins and / or elastomers, and conceptually includes liquid plasticizers (plasticizers that are liquid at 25°C) and solid plasticizers (plasticizers that are solid at 25°C). Specifically, it is a component that can be extracted from its composition using acetone. Such plasticizers can be used alone or in combination of two or more.

[0021] In this document, the group whose interaction with the antifreeze changes with temperature can be any group whose interaction with the antifreeze changes with temperature, and is preferably a group whose interaction with the antifreeze changes reversibly with temperature. Specifically, the group can be a group whose hydrophilicity changes with temperature, preferably a group whose hydrophilicity changes reversibly with temperature. More specifically, the group can be a group whose hydrophilicity changes with temperature at relatively low temperatures (preferably within the preferred temperature range of the phase transition temperature of the temperature-responsive polymer described below), preferably a group whose hydrophilicity changes reversibly with temperature at relatively low temperatures (preferably within the preferred temperature range of the phase transition temperature of the temperature-responsive polymer described below).

[0022] A group whose interaction (hydrophilicity) with the antifreeze changes reversibly with temperature can be a temperature-responsive polymer (temperature-responsive polymer group). In other words, a plasticizer containing a group that changes its interaction with the antifreeze with temperature can refer to a plasticizer containing, for example, groups formed from a temperature-responsive polymer. Examples of such plasticizers include plasticizers grafted with temperature-responsive polymers, plasticizers containing temperature-responsive polymer units in the main chain, and plasticizers containing temperature-responsive polymer blocks in the main chain. They can be used alone or in combination of two or more.

[0023] The term "temperature-responsive polymer" refers to a material that undergoes reversible changes in polymer chain conformation related to hydration and dehydration in response to temperature changes in water, and thus reversibly alters its hydrophilicity and hydrophobicity with temperature variations. This reversible change is known to be caused by a molecular structure comprising hydrophilic groups capable of forming hydrogen bonds and hydrophobic groups that are virtually incompatible with water.

[0024] The inventors then discovered that temperature-responsive polymers can exhibit reversible changes in hydrophilicity and hydrophobicity with temperature, not only in water but also in antifreeze agents (e.g., at low temperatures) or in compositions containing resins and / or elastomers.

[0025] Known temperature-responsive polymers include those exhibiting a lower critical solution temperature (LCST, also known as a lower critical eutectic temperature or lower critical dissolution temperature) in water and those exhibiting an upper critical solution temperature (UCST, also known as an upper critical eutectic temperature or upper critical dissolution temperature) in water. They can be used alone or in combination of two or more.

[0026] Here, when in antifreeze, this temperature-responsive polymer can reversibly change its hydrophilicity and hydrophobicity at the same temperature as it does in water. For example, the LCST of PNIPAM in water is approximately 32°C, and the LCST in antifreeze is also approximately 32°C.

[0027] Polymers exhibiting LCST become hydrophobic at temperatures above the LCST boundary because intramolecular or intermolecular hydrophobic interactions become stronger, leading to polymer chain aggregation. Conversely, at temperatures below the LCST, the polymer chains hydrate by binding with water molecules, becoming hydrophilic. Therefore, the polymers exhibit reversible phase transition behavior near the LCST.

[0028] Conversely, polymers exhibiting UCST become hydrophobic and insoluble below the UCST temperature, and hydrophilic and soluble above the UCST temperature. Therefore, the polymers exhibit reversible phase transition behavior near the UCST. This UCST-type behavior is thought to be caused by intermolecular forces driven by hydrogen bonds between side chains with multiple amide groups.

[0029] When a polymer exhibits LCST (glass transition temperature) and whose functional groups reversibly change their interaction with the antifreeze with temperature changes, the temperature change can lead to incompatibility between the polymer and other components in the composition, thereby altering the glass transition temperature. Therefore, tire performance (e.g., wet grip, ice grip) can be modified in response to temperature changes.

[0030] In plasticizers, groups whose interaction with the antifreeze changes reversibly with temperature are preferably polymers exhibiting a lower critical solution temperature (LCST). In other words, groups whose interaction with the antifreeze changes with temperature are preferably groups that exhibit a lower critical solution temperature in the antifreeze.

[0031] In this article, the group exhibiting the lower critical solution temperature (LCST) in the antifreeze refers to the group present in the plasticizer, and the group exhibits the lower critical solution temperature in the antifreeze when it cleaves from the plasticizer and introduces the cleaved group (polymer) into the antifreeze.

[0032] Similarly, in this article, the group exhibiting the upper critical solution temperature (UCST) in the antifreeze refers to the group present in the plasticizer, and when the group is cleaved from the plasticizer and the cleaved group (polymer) is introduced into the antifreeze, the group exhibits the upper critical solution temperature of the antifreeze.

[0033] In this article, the term "antifreeze" refers to a liquid composed of methanol and water, which can be prepared by mixing water and methanol at 25°C for 30 minutes, with the amount of methanol being 9 times the volume of water.

[0034] The following describes the groups (polymers) that exhibit LCST.

[0035] The groups (polymers) that indicate LCST may contain a single group (polymer) or a combination of two or more groups (polymers).

[0036] The group (polymer) displaying LCST can be any group (polymer) displaying LCST. Preferred is poly(alkyl vinyl ether), more preferably a group represented by formula (I). Also preferred is a group represented by formula (II). In this case, it is preferable to achieve the beneficial effect more appropriately. They can be used alone or in combination of two or more.

[0037] [Chemistry 1]

[0038]

[0039] In the formula, n represents an integer from 1 to 1000; R 1 R 2 and R 3Each can be represented independently as a hydrogen atom or a hydrocarbon group.

[0040] Preferably, n is 3 or more, more preferably 5 or more, even more preferably 10 or more, particularly preferably 20 or more, but preferably 500 or less, more preferably 300 or less, even more preferably 150 or less, particularly preferably 80 or less, most preferably 40 or less, and even more preferably 30 or less. When n is within the above-described range, the beneficial effects tend to be better achieved.

[0041] R 1 The hydrocarbon group may have any number of carbon atoms. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, but preferably 20 or less, more preferably 18 or less, even more preferably 14 or less, particularly preferably 10 or less, most preferably 6 or less, and even more preferably 4 or less. When the number of carbon atoms is within the range mentioned above, the beneficial effects are better achieved.

[0042] R 2 and R 3 The hydrocarbon group can have any number of carbon atoms. The number of carbon atoms is preferably 1 or more, but preferably 5 or less, more preferably 3 or less, even more preferably 2 or less, and particularly preferably 1. When the number of carbon atoms is within the range mentioned above, the beneficial effects are better achieved.

[0043] R 1 R 2 and R 3 Examples of hydrocarbon groups include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, and n-hexyl; cycloalkyl groups such as cyclohexyl; and aryl groups such as methylphenyl and ethylphenyl. Alkyl and cycloalkyl groups are preferred among these, and alkyl groups are more preferred.

[0044] Preferably, R 1 It is an alkyl group, R 2 and R 3 It is a hydrogen atom. More preferably, R 1 It is ethyl, R 2 and R 3 It is a hydrogen atom.

[0045] Examples of groups in formula (I) include poly(methyl vinyl ether), poly(ethyl vinyl ether), poly(propyl vinyl ether), poly(butyl vinyl ether), poly(pentenyl ether), poly(hexyl vinyl ether), poly(heptyl vinyl ether), and poly(octyl ether). They can be used alone or in combination of two or more. Poly(ethyl vinyl ether) (PEVE) is preferred among these. Extensive research by the inventors has shown that the LCST of PEVE is -10°C to +10°C. Therefore, when plasticizers containing PEVE groups (whose surface properties change from hydrophilic to hydrophobic at -10°C to +10°C) are used as plasticizers for resins and / or elastomers, the plasticizers can modify tire performance within the temperature range required by the tire and can also be used to prepare tire compositions.

[0046] Next, the groups of formula (II) will be described.

[0047] [Chemistry 2]

[0048]

[0049] In the formula, n represents an integer from 1 to 1000; R4 represents n-butyl or tert-butyl; R 5 It represents a hydrogen atom or a hydrocarbon group.

[0050] Preferably, n is 3 or more, more preferably 5 or more, even more preferably 10 or more, particularly preferably 20 or more, but preferably 500 or less, more preferably 300 or less, even more preferably 150 or less, particularly preferably 80 or less, most preferably 40 or less, and even more preferably 30 or less. When n is within the ranges mentioned above, the beneficial effects will be better achieved.

[0051] R 4 It is n-butyl or tert-butyl, preferably tert-butyl.

[0052] R 5 The hydrocarbon group can have any number of carbon atoms. The number of carbon atoms is preferably 1 or more, but preferably 5 or less, more preferably 3 or less, even more preferably 2 or less, and particularly preferably 1. When the number of carbon atoms is within the range mentioned above, the beneficial effects are better achieved.

[0053] R 5 Examples of hydrocarbon groups include R 1 R 2 and R 3 Of those listed, alkyl groups are preferred.

[0054] R 5 It can be a branched or unbranched hydrocarbon group.

[0055] R 5 Preferably, it is a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

[0056] Preferably, R 4 It is n-butyl or tert-butyl, R 5 It is a hydrogen atom. More preferably, R 4 For tert-butyl, R 5 It is a hydrogen atom.

[0057] Examples of groups in formula (II) include poly(N-n-butylacrylamide), poly(N-tert-butylacrylamide), poly(N-n-butylmethylacrylamide), and poly(N-tert-butylmethylacrylamide). They can be used alone or in combination of two or more. Poly(N-n-butylacrylamide) or poly(N-tert-butylacrylamide) is preferred. Extensive research by the inventors has shown that the LCST of poly(N-n-butylacrylamide) and poly(N-tert-butylacrylamide) is -10°C to +10°C. Therefore, when a plasticizer containing poly(N-n-butylacrylamide) or poly(N-tert-butylacrylamide) groups (whose surface properties change from hydrophilic to hydrophobic at -10°C to +10°C) is used as a plasticizer for resins and / or elastomers, the plasticizer can modify tire performance within the temperature range required by the tire and can also be used to prepare tire compositions.

[0058] Examples of groups exhibiting LCST other than those mentioned above include copolymers of N-isopropylacrylamide and butyl acrylate, block copolymers of N-isopropylacrylamide and polyethylene oxide, copolymers of N-isopropylacrylamide and fluorinated monomers, copolymers of 2-methaneoxyethyl acrylate and N,N-dimethylacrylamide, biotin-fixed temperature-responsive magnetic microparticles (microparticles generated by the reaction of N-acryloylglycine, methacrylic acid magnetic microparticles, and biotin monomers), copolymers of ethylene oxide and propylene oxide, monoamine products of ethylene oxide and propylene oxide copolymers, polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymers, maltopentose-modified polypropylene oxide, copolymers of 2-methaneoxyethyl acrylate and acryloylmorpholine, and copolymers of 2-methaneoxyethyl acrylate and N-vinylpyrrolidone. Copolymers of 2-methaneoxyethyl acrylate and 2-hydroxyethyl acrylate, copolymers of 2-methaneoxyethyl acrylate and ethylene glycol acrylate, poly[2-(2-ethoxyethoxy)ethyl acrylate], poly(2-(2-ethoxyethoxy)ethyl acrylate-crosslinked-2-(methoxyethoxy)methyl acrylate), copolymers of N-vinylcaprolactam and hydroxyethyl methacrylate, copolymers of methyl vinyl ether and hydroxyethyl methacrylate, poly(1-n-propyl-3-vinyl-2-imidazolone), poly(N-vinyl-2-imidazolone compounds), copolymers of 2-hydroxyethyl vinyl ether and vinyl acetate, copolymers of diethylene glycol monovinyl ether and vinyl acetate, magnetic nanoparticles, and polystyrene and glycourea polymers containing amino groups. These can be used alone or in combination of two or more.

[0059] Here, each group whose interaction with the antifreeze changes with temperature, temperature-responsive polymer group, group (polymer) exhibiting LCST, poly(alkyl vinyl ether) and group of formula (I) preferably does not include the following compound (group): polyethylene methyl ether (poly(methyl vinyl ether)).

[0060] Furthermore, plasticizers for resins and / or elastomers that contain groups whose interaction with antifreeze changes with temperature preferably do not include the following plasticizers.

[0061] (1) The plasticizer (PNIPAM-PS resin) obtained as described below.

[0062] 11.32 g of N-isopropylacrylamide (NIPAM monomer) was added to a nitrogen-purged glass flask, followed by 25 mL of toluene. The mixture was stirred at room temperature for 30 minutes to obtain a homogeneous solution. Then, 1.10 g of 2,2'-azobis(isobutyronitrile) (AIBN) was added to the solution, and the mixture was refluxed for 3 hours. The reaction solution was cooled to 40°C, and then 11.32 g of styrene-acrylic resin (PS, ARUFON UH-2170 (softening point: 80°C), purchased from Toa Synthetic Co., Ltd.) and 25 mL of toluene were added. The mixture was then refluxed for 3 hours. The toluene solvent was then removed from the reaction solution using a rotary evaporator, and the remaining dry solid was dried at 80°C under reduced pressure (below 0.1 Pa) for 8 hours.

[0063] (2) The plasticizer (PNIPAM-BR) obtained as described below.

[0064] 11.32 g of N-isopropylacrylamide (NIPAM monomer) was added to a nitrogen-purged glass flask, followed by 25 mL of toluene. The mixture was stirred at room temperature for 30 minutes to obtain a homogeneous solution. Then, 1.10 g of 2,2'-azobis(isobutyronitrile) (AIBN) was added, and the mixture was refluxed for 3 hours. The reaction solution was cooled to 40°C, and then 11.32 g of maleic acid-modified liquid polybutadiene (Ricon 130MA8 (maleic acid-modified liquid BR, Mw: 2700), purchased from Cray Valley) and 25 mL of toluene were added. The mixture was then refluxed for 3 hours. The toluene solvent was then removed from the reaction solution using a rotary evaporator, and the remaining dry solid was dried at 80°C under reduced pressure below 0.1 Pa for 8 hours.

[0065] Furthermore, groups that change their interaction with the antifreeze with temperature, temperature-responsive polymer groups, and groups (polymers) exhibiting LCST preferably do not include the following compounds (groups):

[0066] The group represented by formula (A) is:

[0067] [Chemistry 3]

[0068]

[0069] In the formula, n represents an integer from 1 to 1000; R 1 R 2 and R 3 Each can independently represent a hydrogen atom or a hydrocarbon group, provided that R... 1 or R 2 At least one of them is not a hydrogen atom, and R 1 and R2 They can form a ring structure together;

[0070] Poly(N-vinylcaprolactam) represented by formula (II);

[0071] Poly(2-alkyl-2-oxazoline) represented by formula (III);

[0072] Alkyl-substituted cellulose;

[0073] Poly(N-ethoxyethylacrylamide);

[0074] Poly(N-ethoxyethyl methacrylamide);

[0075] Poly(N-tetrahydrofuranylacrylamide);

[0076] Poly(N-tetrahydrofurfurylmethacrylamide);

[0077] Polyvinyl methyl ether;

[0078] Poly[2-(dimethylamino)methacrylate ethyl ester];

[0079] Poly(3-ethyl-N-vinyl-2-pyrrolidone);

[0080] Hydroxybutyl chitosan;

[0081] Polyoxyethylene (20) sorbitan monostearate;

[0082] Polyoxyethylene (20) sorbitan monolaurate;

[0083] Polyoxyethylene (20) sorbitan monooleate;

[0084] Poly(ethylene glycol) methacrylates containing 2 to 6 ethylene glycol units;

[0085] Polyethylene glycol-polypropylene glycol;

[0086] Ethoxylated iso-C 13 H 27 -alcohol;

[0087] Polyethylene glycol containing 4 to 50 ethylene glycol units;

[0088] Polypropylene glycol containing 4 to 30 polypropylene glycol units;

[0089] Polyethylene glycol monomethyl ether, dimethyl ether, monoethyl ether, or diethyl ether containing 4 to 50 ethylene glycol units;

[0090] Polypropylene glycol monomethyl ether, dimethyl ether, monoethyl ether, or diethyl ether containing 4 to 50 propylene glycol units.

[0091] [Chemistry 4]

[0092]

[0093] In formulas (II) and (III), n is defined the same as in structural formula (A). In formula (III), R is an alkyl group selected from n-propyl, isopropyl, or ethyl.

[0094] Furthermore, groups that alter their interaction with the antifreeze with temperature, temperature-responsive polymer groups, and groups (polymers) exhibiting LCST preferably do not include the following compounds (groups):

[0095] Poly(N-substituted (meth)acrylamide);

[0096] Poly(N-vinylcaprolactam) represented by the following structural formula (II);

[0097] Poly(2-alkyl-2-oxazoline) represented by structural formula (III);

[0098] Alkyl-substituted cellulose;

[0099] Poly(N-ethoxyethylacrylamide);

[0100] Poly(N-ethoxyethyl methacrylamide);

[0101] Poly(N-tetrahydrofuranylacrylamide);

[0102] Poly(N-tetrahydrofurfurylmethacrylamide);

[0103] Polyvinyl methyl ether;

[0104] Poly[2-(dimethylamino)methacrylate ethyl ester];

[0105] Poly(3-ethyl-N-vinyl-2-pyrrolidone);

[0106] Hydroxybutyl chitosan;

[0107] Polyoxyethylene (20) sorbitan monostearate;

[0108] Polyoxyethylene (20) sorbitan monolaurate;

[0109] Polyoxyethylene (20) sorbitan monooleate;

[0110] Poly(ethylene glycol) methacrylates containing 2 to 6 ethylene glycol units;

[0111] Polyethylene glycol-polypropylene glycol;

[0112] Ethoxylated iso-C 13 H27 -alcohol;

[0113] Polyethylene glycol containing 4 to 50 ethylene glycol units;

[0114] Polypropylene glycol containing 4 to 30 polypropylene glycol units;

[0115] Polyethylene glycol monomethyl ether, dimethyl ether, monoethyl ether, or diethyl ether containing 4 to 50 ethylene glycol units;

[0116] Polypropylene glycol monomethyl ether, dimethyl ether, monoethyl ether, or diethyl ether containing 4 to 50 propylene glycol units.

[0117] [Chemistry 5]

[0118]

[0119] In formulas (II) and (III), n is defined the same as in structural formula (A). In formula (III), R is an alkyl group selected from n-propyl, isopropyl, or ethyl.

[0120] The weight-average molecular weight of the groups whose interaction with the antifreeze changes with temperature (groups formed by temperature-responsive polymers) is preferably 50 or more, more preferably 560 or more, even more preferably 1130 or more, but preferably 57000 or less, more preferably 34000 or less, even more preferably 17000 or less. When the weight-average molecular weight is within the above range, the beneficial effects tend to be better achieved.

[0121] The phase transition temperature (lower critical solution temperature (LCST) or upper critical solution temperature (UCST), especially LCST) of the temperature-responsive polymer is at least -20°C but not higher than 20°C, preferably not higher than 10°C. Beneficial effects tend to be achieved better when the phase transition temperature is within the above range.

[0122] In this paper, the phase transition temperature of the temperature-responsive polymer can be easily determined by preparing 1% polymer / antifreeze from a 90 v / v% methanol aqueous solution (antifreeze), storing the prepared solution in a freezer at a predetermined temperature (e.g., -20°C) or in a refrigerator at a predetermined temperature (e.g., +5°C) for at least 1 hour, and then observing the turbidity of the solution at each temperature.

[0123] Here, temperature-responsive polymer refers to the temperature-responsive polymer group (temperature-responsive polymer) that is cleaved from the plasticizer containing the temperature-responsive polymer group.

[0124] In addition, a 90 v / v% methanol aqueous solution is a liquid composed of methanol and water, which can be prepared by mixing water and methanol at 25°C for 30 minutes, with the amount of methanol being 9 times the volume of water.

[0125] Relative to 100% by mass of the plasticizer, the amount of groups (groups formed by temperature-responsive polymers) that change their interaction with the antifreeze with temperature is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, particularly preferably 10% by mass or more, most preferably 20% by mass or more, even more preferably 30% by mass or more, further most preferably 40% by mass or more, but preferably 99% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, particularly preferably 60% by mass or less, and most preferably 50% by mass or less. When this amount is within the range specified above, beneficial effects tend to be better achieved.

[0126] As stated above, the term "plasticizer containing groups that change their interaction with the antifreeze with temperature" refers, for example, a plasticizer containing groups formed by a temperature-responsive polymer, i.e., a plasticizer combined with groups formed by a temperature-responsive polymer.

[0127] Specifically, plasticizers containing groups that change their interaction with antifreeze with temperature can be oils, ester plasticizers, or solid or liquid resins (hereinafter collectively referred to as "oils or the like"), which contain groups formed by temperature-responsive polymers. They can be used alone or in combination of two or more.

[0128] Oils or similar substances used in conventional applications typically do not contain groups formed by temperature-responsive polymers.

[0129] Therefore, plasticizers can be commercial products (if available) or produced using known synthetic techniques. For example, plasticizers can be produced with reference to JP 2005-314419 A, JP 2016-505679 T, JP 2015-531672 T, JP 2003-252936A, JP 2004-307523 A, etc.

[0130] Exemplary methods for producing plasticizers may include synthesizing the plasticizer using monomeric components capable of forming temperature-responsive polymer units by known methods. For example, once ethyl vinyl ether (EVE) (which is a monomer constituting PEVE (a temperature-responsive polymer)) is added to a plasticizer produced by cationic polymerization, the addition of the temperature-responsive polymer PEVE to the plasticizer structure can be confirmed by increasing the molecular weight.

[0131] Another exemplary method for producing plasticizers may include radically polymerizing and reacting PEVE with a plasticizer component, wherein the plasticizer component may have radicals added thereto according to known methods to synthesize a PEVE-added plasticizer. In other words, the plasticizer can be synthesized from a monomer component capable of forming temperature-responsive polymer units. Therefore, plasticizers having temperature-responsive polymer units in the main chain can be produced.

[0132] For example, to prepare a plasticizer having PEVE units in the main chain, ethyl vinyl ether (which is a monomer constituting PEVE) can be stirred with a free radical generator (such as AIBN) as a monomer component to carry out free radical polymerization, and then subjected to a free radical addition reaction with a liquid or solid resin having double bonds or carboxylic acid groups that are free radical reactive, to produce a resin having PEVE units in the main chain.

[0133] Furthermore, since random copolymers or block copolymers can be produced by appropriately adjusting the polymerization method, this technology can also be used to produce plasticizers that contain temperature-responsive polymer blocks in the main chain.

[0134] The ends of the temperature-responsive polymer are described.

[0135] When a plasticizer containing a temperature-responsive polymer is added, the temperature-responsive polymer forms a main chain or a bond to the main chain at one end, and the other end is usually a hydrogen atom, but it can be bonded to a polymerization initiator (such as azobisisobutyronitrile (AIBN)).

[0136] In the case of plasticizers containing temperature-responsive polymer units in the main chain or plasticizers containing temperature-responsive polymer blocks in the main chain, either end of the temperature-responsive polymer forms another structural unit or is bonded to another structural unit. When the temperature-responsive polymer unit (temperature-responsive polymer block) is present at the end of the molecule, one end is usually a hydrogen atom, but it can be bonded to a polymerization initiator (e.g., azobisisobutyronitrile (AIBN)).

[0137] The following describes oils, ester plasticizers, or solid or liquid resins (hereinafter collectively referred to as "oils or the like"), wherein groups (groups formed by temperature-responsive polymers) are introduced that alter their interaction with antifreeze as temperature changes. They can be used alone or in combination of two or more. Oils or the like incorporating the aforementioned groups are not limited, as long as they are plastic. Examples include oils or the like commonly used as components in tire compounding. Oils or the like incorporating the aforementioned groups are preferably oils or liquid or solid resins, more preferably liquid or solid resins, and even more preferably solid resins.

[0138] Any oil can be used, and examples include conventional oils such as paraffinic processing oils, aromatic processing oils, and naphthenic processing oils; low polycyclic aromatic (PCA) processing oils such as TDAE and MES; vegetable oils; and mixtures thereof. They can be used alone or in combination of two or more. Aromatic processing oils are preferred. Specific examples of aromatic processing oils include the Diana process Oil AH series manufactured by Idemitsu Kosan Co., Ltd.

[0139] Examples of commercial oils include those produced by companies such as Idemitsu Kosan Co., Ltd., Sankyo Oil & Chemical Co., Ltd., Nippon Energy Co., Ltd., Olisoy, H&R, Toyokuni Oil Co., Ltd., Showa Shell Oil Co., Ltd., and Fuji Kosan Co., Ltd.

[0140] Examples of ester plasticizers include the aforementioned vegetable oils; synthetic plasticizers and processed vegetable oils, such as glycerol fatty acid monoesters, glycerol fatty acid diesters, and glycerol fatty acid triesters; and phosphate esters (e.g., phosphate plasticizers and mixtures thereof). They can be used alone or in combination of two or more.

[0141] Suitable examples of ester plasticizers include fatty acid esters represented by the following structural formula:

[0142] [Chemistry 6]

[0143]

[0144] In the formula R 11 Represents C1-C8 straight-chain or branched alkyl, C1-C8 linear or branched alkenyl, or C2-C6 straight-chain or branched alkyl with 1-5 hydroxyl groups; R 12 It indicates C11-C21 alkyl or alkenyl groups.

[0145] R 11 Examples include methyl, ethyl, 2-ethylhexyl, isopropyl, and octyl, as well as groups obtained by substituting these groups with 1 to 5 hydroxyl groups. R 12 Examples include straight-chain or branched alkyl or alkenyl groups, such as lauryl, myristyl, palmityl, stearyl, and oleyl.

[0146] Examples of fatty acid esters include alkyl oleate, alkyl stearate, alkyl linoleate, and alkyl palmitate. Alkyl oleate (e.g., methyl oleate, ethyl oleate, 2-ethylhexyl oleate, isopropyl oleate, octyl oleate) is preferred. In this case, the amount of alkyl oleate is preferably 80% or more, based on 100% by mass of the fatty acid ester.

[0147] Other examples of fatty acid esters include fatty acid monoesters or diesters formed from fatty acids (e.g., oleic acid, stearic acid, linoleic acid, palmitic acid) and alcohols (e.g., ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, erythritol, xylitol, sorbitol, duriol, mannitol, inositol). Oleic acid monoesters are preferred. In this case, the amount of oleic acid monoester is preferably 80% or more, based on a combined amount of 100% by mass of the fatty acid monoester and fatty acid diester.

[0148] Phosphate esters can be appropriately used as ester plasticizers.

[0149] Preferred phosphate esters include C12-C30 compounds, among which C12-C30 trialkyl phosphate esters are suitable. Here, the number of carbon atoms in a trialkyl phosphate ester refers to the total number of carbon atoms in the three alkyl groups. The three alkyl groups can be the same or different groups. Examples of alkyl groups include straight-chain or branched alkyl groups, which may contain heteroatoms (such as oxygen atoms) or be substituted with halogen atoms (such as fluorine, chlorine, bromine, or iodine).

[0150] Other examples of phosphate esters include known phosphate ester plasticizers, such as monoesters, diesters, or triesters of phosphoric acid with C1-C12 monools or their (poly)oxyalkylene adducts; and compounds obtained by substituting one or two alkyl groups of the above-mentioned trialkyl phosphates with phenyl groups. Specific examples include tri(2-ethylhexyl) phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate, tricresyl phosphate, diphenyl phosphate, diethylhexyl diphenylphosphate, and tri(2-butoxyethyl) phosphate.

[0151] Examples of solid resins include resins that are solid at 25°C, such as terpene resins (including rosin resins), styrene resins, C5 resins, C9 resins, C5 / C9 resins, coumarone-indene resins (including resins based on a single coumarone or a single indene), olefin resins, urethane resins, acrylic resins, p-tert-butylphenol-acetylene resins, and dicyclopentadiene resins (DCPD resins). These resins can be hydrogenated. They can be used alone or in mixtures of two or more. Furthermore, the resin itself can be a copolymer of monomer components from different sources. Styrene resins and terpene resins are preferred, with styrene resins being more preferred.

[0152] Examples of commercially available solid resins include those produced by Maruzen Petrochemical Co., Ltd., Sumitomo Bakelite Co., Ltd., Yasuhara Chemical Co., Ltd., Tosoh Co., Ltd., Rutgers Chemicals, BASF, Arizona Chemical Company, Nitto Kasei Corporation, Nippon Shokubai Co., Ltd., JXTG Energy Co., Ltd., Arakawa Chemical Co., Ltd., and Taoka Chemical Co., Ltd.

[0153] The softening point of the solid resin is preferably 30°C or higher, more preferably 60°C or higher, even more preferably 80°C or higher, but preferably 200°C or lower, more preferably 160°C or lower, even more preferably 140°C or lower, and particularly preferably 120°C or lower. When the softening point is within the above-specified range, beneficial effects tend to be achieved more appropriately.

[0154] In this paper, the softening point of the resin was determined using a ring and ball softening point measuring device according to the specifications in JIS K 6220-1∶2001, and was defined as the temperature at which the ball falls.

[0155] Terpene resins can be any resin containing units derived from terpene compounds, and examples include polyterpenes (resins produced by polymerizing terpene compounds), aromatic terpene resins (resins produced by copolymerizing terpene compounds and aromatic compounds), and aromatic-modified terpene resins (resins obtained by modifying terpene resins with aromatic compounds). Polyterpenes are preferred.

[0156] Terpenes are compounds that possess the properties of (C5H8) n The composition represents hydrocarbons or their oxygen-containing derivatives, each of which has a terpene backbone and is classified, for example, as monoterpenes (C14-C2 ... 10 H 16 ), sesquiterpenes (C 15 H 24 ) or diterpenes (C 20 H 32 Examples of terpenoid compounds include α-pinene, β-pinene, dipentene, limonene, myrcene, allocarmine, ocimene, α-phellandrene, α-terpinene, γ-terpinene, isoterpinene, 1,8-cineole, 1,4-cineole, α-terpineol, β-terpineol, and γ-terpineol. Other examples of terpenoid compounds include resin acids (rosin acids), such as abietic acid, neorosinic acid, longleaf abietic acid, L-piperidine, abietic acid, and isopiratic acid. In other words, terpene resins include rosin resins formed primarily of abietic acid (which is produced by processing pine resin). Examples of rosin resins here include natural rosin resins (polymerized rosin), such as gum rosin, wood rosin and tall oil rosin; modified rosin resins, such as maleic acid modified rosin and rosin modified phenolic resin; rosin esters such as rosin glycerol ester; and disproportionated rosin resins obtained by disproportionation of rosin resins.

[0157] Among terpenoid compounds, α-pinene and β-pinene are preferred, with β-pinene being more preferred. Therefore, among polyterpenoids, poly(α-pinene) and poly(β-pinene) are preferred, with poly(β-pinene) being more preferred.

[0158] Aromatic compounds can be any compound having an aromatic ring. Examples include phenolic compounds, such as phenol, alkylphenol, alkoxyphenol, and phenols containing unsaturated hydrocarbon groups; naphthol compounds, such as naphthol, alkylnaphthol, alkoxynaphthol, and unsaturated hydrocarbon groups containing naphthol; and styrene and styrene derivatives, such as alkylstyrene, alkoxystyrene, and styrene containing unsaturated hydrocarbon groups. Styrene is preferred.

[0159] Styrene resin refers to a polymer formed from styrene monomers as structural monomers, and examples include polymers polymerized with styrene monomers as the main component (50% by mass or more, preferably 80% by mass or more). Specific examples include homopolymers polymerized from a single styrene monomer (e.g., styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, and p-chlorostyrene), copolymers copolymerized from two or more styrene monomers, and copolymers of styrene monomers with other monomers that can be copolymerized therewith. Homopolymers polymerized from a single styrene monomer are preferred.

[0160] Examples of other monomers include acrylonitriles, such as acrylonitrile and methacrylonitrile; unsaturated carboxylic acids, such as acrylic acid and methacrylic acid; unsaturated carboxylic acid esters, such as methyl acrylate and methyl methacrylate; dienes, such as chloroprene, butadiene and isoprene; alkenes, such as 1-butene and 1-pentene; and α-unsaturated carboxylic acids, β-unsaturated carboxylic acids and their anhydrides, such as maleic anhydride.

[0161] The styrene resin is preferably a homopolymer polymerized from a single styrene monomer. More preferably, it is a styrene homopolymer, o-methylstyrene homopolymer, m-methylstyrene homopolymer, p-methylstyrene homopolymer, and α-methylstyrene homopolymer, and even more preferably, it is a styrene homopolymer or an α-methylethylene homopolymer.

[0162] Among styrene resins, α-methylstyrene resins (e.g., α-methylethylene homopolymers, copolymers of α-methylbenzene and styrene) are also preferred.

[0163] Liquid resins with a structure similar to solid resins and a low softening point can be used. Examples include resins that are liquid at 25°C, such as terpene resins (including rosin resins), styrene resins, C5 resins, C9 resins, C5 / C9 resins, coumarone-indene resins (including resins based on a single coumarone or a single indene), olefin resins, urethane resins, acrylic resins, p-tert-butylphenol-acetylene resins, and dicyclopentadiene resins (DCPD resins). These resins can be hydrogenated. They can be used alone or in mixtures of two or more. Furthermore, the resin itself can be a copolymer of monomer components from different sources. Styrene resins are preferred. Preferred embodiments of styrene resins are the same as those described for styrene resins as solid resins. In other words, except that styrene resins have different molecular weights, the preferred embodiments are the same as for solid resins.

[0164] In addition, other examples of liquid resins include liquid (referring to liquid at 25°C, the same below) farnesene polymers, such as liquid farnesene homopolymers, liquid farnesene-styrene copolymers, liquid farnesene-butadiene copolymers, liquid farnesene-styrene-butadiene copolymers, liquid farnesene-isoprene copolymers, and liquid farnesene-styrene-isoprene copolymers; and liquid myrcene polymers, such as liquid myrcene homopolymers, liquid myrcene-styrene copolymers, liquid myrcene-butadiene copolymers, liquid myrcene-styrene-butadiene copolymers, liquid myrcene-isoprene copolymers, and liquid myrcene-styrene-isoprene copolymers. Liquid diene polymers, such as liquid styrene-butadiene copolymer (liquid SBR), liquid polybutadiene polymer (liquid BR), liquid polyisoprene polymer (liquid IR), liquid styrene-isoprene copolymer (liquid SIR), liquid styrene-butadiene-styrene block copolymer (liquid SBS block copolymer), and liquid styrene-isoprene-styrene block copolymer (liquid SIS block copolymer); liquid olefin polymers containing olefin resins (e.g., polyethylene, polypropylene) as hard segments (hard phase) and rubber components as soft segments (soft phase); and liquid ester polymers containing polyester as hard segments and polyethers, polyesters, etc., as soft segments. They can be modified with polar groups at the chain ends or along the main chain. They can be used alone or in combination of two or more. Liquid BR is preferred.

[0165] The weight-average molecular weight of the liquid resin is preferably less than 100,000, more preferably less than 80,000, even more preferably less than 50,000, but preferably more than 500, and more preferably more than 2,000. When the weight-average molecular weight is within the above range, the beneficial effects tend to be achieved better.

[0166] Examples of commercially available liquid resins include those produced by Maruzen Petrochemical Co., Ltd., Sumitomo Bakelite Co., Ltd., Yasuhara Chemical Co., Ltd., Tosoh Co., Ltd., Rutgers Chemicals, BASF, Arizona Chemical Company, Nitto Kasei Corporation, Nippon Shokubai Co., Ltd., JXTG Energy Co., Ltd., Arakawa Chemical Co., Ltd., Taoka Chemical Co., Ltd., Sartomer, Kuraray Co., Ltd., and others.

[0167] Plasticizers containing groups that change their interaction with the antifreeze with temperature are preferably plasticizers containing groups that exhibit a lower critical solution temperature in the antifreeze, more preferably plasticizers containing poly(alkyl vinyl ethers), even more preferably plasticizers containing groups of formula (I), and particularly preferably plasticizers containing poly(ethyl vinyl ethers). Plasticizers containing groups of formula (II) are also preferred.

[0168] Furthermore, in the plasticizer, it is preferable to introduce the group into a solid resin or a liquid resin, more preferably into a solid resin. The solid resin is more preferably a styrene resin or a terpene resin (preferably styrene resin), and even more preferably an ethylene homopolymer, an α-methylstyrene homopolymer, or a polyterpene (preferably a styrene homopolymer or an α-methylethylene homopolymer). The liquid resin is more preferably a styrene resin or a liquid polybutadiene polymer (liquid BR).

[0169] Plasticizers containing groups that change their interaction with antifreeze as temperature changes are plasticizers used in resins and / or elastomers.

[0170] There are no restrictions on the resins to which plasticizers can be applied. In addition to the resins mentioned above, examples include thermoplastic resins such as polycarbonate resins, polyester resins, polyester carbonate resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethersulfone resins, polyaryl resins, polyamide resins, polyetherimide resins, polyacetal resins, polyvinyl alcohol acetal resins, polyketone resins, polyetherketone resins, polyetheretherketone resins, polyaryl ketone resins, polyetheretherketone nitrile resins, liquid crystal resins, polybenzimidazole resins, poly(p-hydroxybenzoic acid) resins, polyolefin resins, vinyl chloride resins, and cellulose resins; and thermosetting resins such as epoxy resins, polyamide-imide resins, thermosetting polyester resins (unsaturated polyester resins), silicone resins, urethane resins, (meth)acrylic resins, fluoropolymers, phenolic resins, urea resins, melamine resins, polyimide resins, alkyd resins, polyethylene terephthalate resins, diallyl phthalate, bismaleimide triazine resins, furan resins, xylene resins, guanidine resins, maleic resins, and polyether resins. They can be used individually or in combination of two or more.

[0171] There are no restrictions on the elastomers to which plasticizers can be applied. Examples include diene rubbers commonly used as rubber components in tire compositions, such as isoprene rubbers, polybutadiene rubber (BR), styrene-butadiene rubber (SBR), styrene-isoprene-butadiene rubber (SIBR), ethylene-propylene-diene rubber (EPDM), chloroprene rubber (CR), and acrylonitrile-butadiene rubber (NBR); acrylic rubbers, such as butyl acrylate rubber, ethyl acrylate rubber, and octyl acrylate rubber; nitrile rubber, isobutylene rubber, methyl methacrylate-butyl acrylate block copolymers, ethylene-propylene copolymers (EPR), chlorosulfonated polyethylene, silicone rubbers (abrasive type, room temperature vulcanizing type), butyl rubber, fluororubber, olefin-based thermoplastic elastomers, and styrene. These are thermoplastic elastomers, including urethane-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, fluorinated thermoplastic elastomers, styrene-isobutylene-styrene block copolymers (SIBS), styrene-isoprene-styrene copolymers (SIS), styrene-isobutylene block copolymers (SIB), styrene-butadiene-styrene block copolymers (SBS), styrene-ethylene / butene-styrene block copolymers (SEBS), styrene-ethylene / propylene-styrene block copolymers (SEPS), styrene-ethylene / ethylene / propylene-styrene block copolymers (SEEPS), and styrene-butadiene / butene-styrene block copolymers (SBBS). They can be used alone or in combination of two or more.

[0172] Among resins and elastomers to which plasticizers can be applied, rubber is preferred, diene rubber is more preferred, and isoprene rubber, BR and SBR are even more preferred.

[0173] (Composition)

[0174] Next, compositions containing plasticizers are described (plasticizers contain groups that change their interaction with the antifreeze as the temperature changes).

[0175] Here, the plasticizer contained in the composition can be identified, for example, by the following methods.

[0176] The composition can be continuously extracted with tetrahydrofuran solvent at room temperature using a Soxhlet extractor for 24 hours, and the extract residues can be separated based on molecular weight by gel permeation chromatography (GPC) or liquid chromatography-mass spectrometry (LC-MS), followed by NMR analysis to identify the compounds.

[0177] The amount of the plasticizer in the composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, even more preferably 3 parts by mass or more, particularly preferably 5 parts by mass or more, most preferably 10 parts by mass or more, further most preferably 20 parts by mass or more, but preferably 200 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 80 parts by mass or less, particularly preferably 60 parts by mass or less, and most preferably 50 parts by mass or less. When this amount is within the above-specified range, the beneficial effects tend to be better achieved.

[0178] The plasticizers described above can be used in conjunction with other plasticizers. Examples of such plasticizers, other than those described above, include the oils or similar substances into which the aforementioned groups are introduced. They can be used alone or in combination of two or more.

[0179] The total amount of plasticizer (the combined amount of the above-mentioned plasticizer and other plasticizers besides the above-mentioned plasticizer) is the same as the amount of the above-mentioned plasticizer.

[0180] Here, the amount of plasticizer includes the amount of plasticizer contained in the rubber (oil-extended rubber) or sulfur (oil-containing sulfur), if used.

[0181] Examples of polymeric components that can be used in the composition include the aforementioned resins and elastomers to which the plasticizers described above can be applied. They can be used alone or in combination of two or more. Rubbers are preferred, diene rubbers are more preferred, isoprene-based rubbers, BR and SBR are even more preferred.

[0182] Here, the polymer component (preferably the rubber component) preferably has a weight-average molecular weight (Mw) of 200,000 or more, more preferably 350,000 or more. There is no upper limit to the Mw, but it is preferably 4,000,000 or less, more preferably 3,000,000 or less.

[0183] In this study, Mw and number-average molecular weight (Mn) were determined by gel permeation chromatography (GPC) calibrated with polystyrene standards (GPC-8000 series from Tosoh Corporation, detector: differential refractometer, column: TSKGEL SUPERMULTIPORE HZ-M from Tosoh Corporation).

[0184] The amount of diene rubber is preferably 20% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and can be 100% by mass, based on a polymer component content of 100% by mass (preferably based on a rubber component content of 100% by mass). When this amount is within the range specified above, the beneficial effects tend to be better achieved.

[0185] The polymer component can be an unmodified or modified polymer.

[0186] The modified polymer can be any polymer (preferably any diene rubber) having functional groups that interact with fillers (such as silica). Examples include end-chain modified polymers obtained by modifying at least one end of the polymer with a compound (modifier) ​​having functional groups (i.e., end-chain modified polymers with functional group-terminated ends); main-chain modified polymers having functional groups in the main chain; main-chain and end-chain modified polymers having functional groups in both the main chain and the chain ends (e.g., main-chain and end-chain modified polymers having functional groups in the main chain and at least one chain end modified by a modifier); and end-chain modified polymers that introduce hydroxyl or epoxy groups by modification (coupling) with a polyfunctional compound having two or more epoxy groups in the molecule.

[0187] Examples of functional groups include amino, amide, silyl, alkoxysilyl, isocyanate, imino, imidazo, urea, ether, carbonyl, oxycarbonyl, mercapto, thioether, dithioether, sulfonyl, sulfinyl, thiocarbonyl, ammonium, imide, hydrazine, azo, diazo, carboxyl, nitrile, pyridinyl, alkoxy, hydroxy, oxygen, and epoxy. These functional groups can be substituted. Preferably, amino groups (preferably amino groups with hydrogen atoms substituted by C1-C6 alkyl groups), alkoxy groups (preferably C1-C6 alkoxy groups), and alkoxysilyl groups (preferably C1-C6 alkoxysilyl groups).

[0188] Any type of SBR can be used. Examples include emulsion polymerized styrene-butadiene rubber (E-SBR) and solution polymerized styrene-butadiene rubber (S-SBR). They can be used alone or in combination of two or more.

[0189] The styrene content of the SBR is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, particularly preferably 20% by mass or more, and most preferably 25% by mass or more. The styrene content is also preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, particularly preferably 40% by mass or less, and most preferably 35% by mass or less. When the styrene content is within the above-specified range, beneficial effects are more likely to be achieved.

[0190] In this article, the styrene content of SBR can be determined by... 1 H-NMR analysis was performed.

[0191] SBR products manufactured or sold by companies such as Sumitomo Chemical Co., Ltd., JSR Co., Ltd., Asahi Kasei Corporation, and Zeon Corporation can be used as SBR.

[0192] SBRs can be unmodified or modified. Examples of modified SBRs include those modified polymers in which the listed functional groups are introduced. Modified SBRs are preferred.

[0193] Any type of bioreactor (BR) can be used. Examples include high-cis BR with a high cis content, BR containing isotactic polybutadiene crystals, and BR synthesized using rare earth catalysts (rare earth-catalyzed BR). They can be used alone or in combination of two or more. In particular, to improve wear resistance, high-cis BR with a cis content of 90% by mass or more is preferred. Here, the cis content can be measured by infrared absorption spectroscopy.

[0194] Furthermore, the BR can be unmodified or modified. Examples of modified BR include those in which functional groups listed for the modified polymer are introduced.

[0195] Examples of commercially available BR include those produced by Ube Industries, Ltd., JSR Corporation, Asahi Kasei Corporation, and Zeon Corporation.

[0196] Examples of isoprene-based rubbers include natural rubber (NR), polyisoprene rubber (IR), refined NR, modified NR, and modified IR. Examples of NR include rubbers commonly used in the tire industry, such as SIR20, RSS#3, and TSR20. Any IR can be used, including, for example, IR2200 commonly used in the tire industry. Examples of refined NR include deproteinized natural rubber (DPNR) and high-purity natural rubber (UPNR). Examples of modified NR include epoxidized natural rubber (ENR), hydrogenated natural rubber (HNR), and grafted natural rubber. Examples of modified IR include epoxidized polyisoprene rubber, hydrogenated polyisoprene rubber, and grafted polyisoprene rubber. They can be used alone or in combination of two or more. NR is preferred.

[0197] Based on a polymer component content of 100% by mass (preferably based on a rubber component content of 100% by mass), the amount of SBR is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 40% by mass or more, and particularly preferably 60% by mass or more. This amount can be 100% by mass, but is preferably 90% by mass or less, more preferably 80% by mass or less. When this amount is within the range specified above, it tends to achieve better beneficial effects.

[0198] Based on a polymer component content of 100% by mass (preferably based on a rubber component content of 100% by mass), the amount of BR is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. This amount can be 100% by mass, but is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less. When this amount is within the range specified above, it tends to achieve better beneficial effects.

[0199] Based on a polymer component content of 100% by mass (preferably based on a rubber component content of 100% by mass), the amount of isoprene-based rubber is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, particularly preferably 4% by mass or more, and most preferably 10% by mass or more. This amount can be 100% by mass, but is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less. When this amount is within the above-specified range, it tends to achieve better beneficial effects.

[0200] Furthermore, multicomponent copolymers comprising conjugated diene units, non-conjugated olefin units, and aromatic vinyl units are preferably present as rubber components. In this case, it is preferable to achieve beneficial effects more appropriately.

[0201] The conjugated diene units in multicomponent copolymers are structural units derived from conjugated diene compounds. Examples of conjugated diene compounds include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene. They can be used alone or in combination of two or more. 1,3-Butadiene and isoprene are preferred, with 1,3-butadiene being more preferred.

[0202] The non-conjugated olefin units in the multicomponent copolymer are structural units derived from non-conjugated olefins. Examples of non-conjugated olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. They can be used alone or in combination of two or more. Ethylene, propylene, and 1-butene are preferred, and ethylene is more preferred.

[0203] The aromatic vinyl units in the multicomponent copolymer are structural units derived from aromatic vinyl compounds. Examples of aromatic vinyl compounds include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, vinylethylbenzene, divinylbenzene, 4-cyclohexylstyrene, and 2,4,6-trimethylstyrene. They can be used alone or in combination of two or more. Styrene and α-methylstyrene are preferred, and styrene is more preferred.

[0204] For example, multicomponent copolymers can be prepared by copolymerizing conjugated dienes, non-conjugated olefins, and aromatic vinyl compounds, or by copolymerizing a combination of conjugated dienes and aromatic compounds, or a combination of conjugated dienes, non-conjugated olefins, and aromatic alkenyl compounds, and then hydrogenating the copolymer to convert some of the conjugated diene units into non-conjugated olefin units. In other words, multicomponent copolymers can be copolymers of conjugated dienes, non-conjugated olefins, and aromatic vinyl compounds, or hydrogenated products of copolymers of conjugated dienes and aromatic compounds (hydrogenated copolymers), or copolymers of conjugated dienes, non-conjugated olefins, and aromatic vinyl compounds (hydrogenated copolymers). Each of these copolymers can be used alone, or two or more can be used in combination. Preferably, the multicomponent copolymer is a hydrogenated product of a copolymer of conjugated dienes and aromatic vinyl compounds, more preferably a hydrogenated styrene-butadiene copolymer (hydrogenated SBR).

[0205] Multicomponent copolymers can be prepared by any polymerization method, such as random polymerization or block polymerization, preferably by random polymerization.

[0206] When the multicomponent copolymer is a hydrogenated copolymer, hydrogenation can be carried out by any method under any reaction conditions, including known methods and conditions. Typically, hydrogenation is carried out in the presence of a hydrogenation catalyst at 20 to 150°C and elevated hydrogen pressures of 0.1 to 10 MPa. Other methods and conditions related to the production process are also not limited; for example, those methods and conditions described in WO 2016 / 039005 above may be used.

[0207] When the multicomponent copolymer is a hydrogenated copolymer, the degree of hydrogenation is preferably 65 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, but preferably 95 mol% or less, more preferably 94.5 mol% or less, and even more preferably 94 mol% or less. When the degree of hydrogenation is within the above-specified range, beneficial effects are more likely to be achieved.

[0208] Here, the degree of hydrogenation can be determined according to... 1 The calculation is based on the rate of decrease in the unsaturated bond signal measured in the H-NMR spectrum.

[0209] Based on 100 mol% of the total structural units of the multicomponent copolymer, the content of conjugated diene units is preferably 1.9 mol% or more, more preferably 2.4 mol% or more, even more preferably 2.9 mol% or more, but preferably 23.7 mol% or less, more preferably 16.9 mol% or less, even more preferably 10.7 mol% or less. When the content is within the above-specified range, the beneficial effects tend to be better achieved.

[0210] Based on 100 mol% of the total structural units of the multicomponent copolymer, the content of non-conjugated olefin units is preferably higher than 65 mol%, more preferably 70 mol% or more, even more preferably 80 mol% or more, but preferably lower than 95 mol%, more preferably 94.5 mol% or less, even more preferably 94 mol% or less. When the content is within the above-specified range, the beneficial effects tend to be better achieved.

[0211] Based on 100 mol% of the total structural units of the multicomponent copolymer, the content of aromatic vinyl units is preferably 4 mol% or more, more preferably 8 mol% or more, but preferably 45 mol% or less, more preferably 40 mol% or less, even more preferably 35 mol% or less, particularly preferably 25 mol% or less, and most preferably 20 mol% or less. When the content is within the above-specified range, the beneficial effects tend to be better achieved.

[0212] The structural unit content of the multicomponent copolymer was measured by NMR.

[0213] The weight-average molecular weight (Mw) of the multicomponent copolymer is preferably 100,000 or more, more preferably 150,000 or more, even more preferably 200,000 or more, particularly preferably 400,000 or more, but preferably 2,000,000 or less, more preferably 1,500,000 or less, even more preferably 1,000,000 or less, and particularly preferably 600,000 or less. When Mw is within the above-specified range, the beneficial effects tend to be better achieved.

[0214] Based on a rubber component content of 100% by mass, the amount of the multicomponent copolymer is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 40% by mass or more, and particularly preferably 60% by mass or more. This amount can be 100% by mass, but is preferably 90% by mass or less, more preferably 80% by mass or less. When this amount is within the range specified above, it tends to achieve better beneficial effects.

[0215] The composition preferably contains silica as a filler (reinforcing filler).

[0216] Any type of silica can be used, including dry silica (anhydrous silicic acid) and wet silica (hydrated silicic acid). They can be used alone or in combination of two or more. Wet silica is preferred because it has a large number of silanol groups.

[0217] Examples of commercially available silica include silica purchased from companies such as Degussa, Rhodia, Tosoh Silicon Chemicals Co., Ltd., Solvay Japan, and Tokuyama Corporation.

[0218] The nitrogen adsorption specific surface area (N2SA) of silica is preferably 50 m² / s. 2 / g or more, preferably 150m 2 / g or more. N2SA is preferably 300mg / g. 2 / g or less, more preferably 250m 2 Below / g, and more preferably 200m 2 / g or less. When N2SA is within the range specified above, it tends to achieve better beneficial effects.

[0219] Here, the N2SA of silica can be measured according to ASTM D3037-81.

[0220] The amount of silica is preferably 0.1 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 30 parts by mass or more, particularly preferably 50 parts by mass or more, but preferably 200 parts by mass or less, more preferably 180 parts by mass or less, even more preferably 150 parts by mass or less, and particularly preferably 120 parts by mass or less, relative to 100 parts by mass of polymer component content (preferably relative to 100 parts by mass of rubber component content). When this amount is within the above-specified range, the beneficial effects tend to be better achieved.

[0221] The ratio of the amount of silica (in parts by mass) to the average primary particle size of silica (in nm) relative to 100 parts by mass of polymer component content (preferably relative to 100 parts by mass of rubber component content) is preferably 0.01 or more, more preferably 0.1 or more, even more preferably 1 or more, but preferably 2000 or less, more preferably 1500 or less, even more preferably 1000 or less, particularly preferably 100 or less, most preferably 10 or less, and even more preferably 5 or less. When this ratio is within the range specified above, beneficial effects tend to be achieved better.

[0222] In this paper, the average primary particle size of silica can be determined by measuring the particle size of at least 400 primary silica particles observed in the field of view of a transmission or scanning electron microscope and averaging them.

[0223] When the composition contains silica, it preferably contains a silane coupling agent together with the silica.

[0224] Any silane coupling agent can be used. Examples include sulfide silane coupling agents, such as bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilyl)tetrasulfide, bis(4-triethoxysilyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(2-triethoxysilylethyl)trisulfide, and bis(4-trimethoxysilylbutyl)trisulfide. Bis(3-triethoxysilylpropyl) disulfide, bis(2-triethoxysilylethyl) disulfide, bis(4-triethoxysilyl) disulfide, bis(3-trimethoxysilylpropyl) disulfide, bis(2-trimethoxysilylethyl) disulfide, bis(4-trimethoxysilyl) disulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide 2-Triethoxysilyl-N,N-dimethylthiocarbamoyl tetrasulfide and 3-triethoxysilylpropyl methacrylate monosulfide; mercaptosilane coupling agents, such as 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, NXT and NXT-Z (all available from Momentive); vinylsilane coupling agents, such as vinyltriethoxysilane and vinyltrimethoxysilane; aminosilane coupling agents. Coupling agents, such as 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane; glycidyl silane coupling agents, such as γ-glycidylpropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane; nitrosilane coupling agents, such as 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane; and chlorosilane coupling agents, such as 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane. They can be used alone or in combination of two or more.

[0225] Examples of commercially available silane coupling agents include those purchased from Degussa, Momentive, Shin-Etsu Silicones Co., Ltd., Tokyo Chemical Industry Co., Ltd., AZmax Co., Ltd., Dow Corning Toray Industries, Ltd., etc.

[0226] The amount of silane coupling agent (if present) relative to 100 parts by mass of silica is preferably 0.1 parts by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more. This amount is also preferably 20 parts by mass or less, more preferably 16 parts by mass or less, and even more preferably 12 parts by mass or less. When this amount is within the above range, beneficial effects are more likely to be achieved.

[0227] The composition preferably contains carbon black.

[0228] Examples of carbon black include N134, N110, N220, N234, N219, N339, N330, N326, N351, N550, and N762. They can be used alone or in combination of two or more.

[0229] The nitrogen adsorption specific surface area (N2SA) of carbon black is preferably 5m². 2 / g or more, preferably 30m 2 / g or more, more preferably 60m² / g or more, particularly preferably 90m² / g or more. 2 / g or more, the optimal value is 120m 2 / g or more. N2SA is also preferably 300m. 2 / g or less, more preferably 200m 2 / g or less, and more preferably 170m 2 / g or less. When N2SA is within the range specified above, it tends to achieve better beneficial effects.

[0230] Here, the nitrogen adsorption specific surface area of ​​carbon black can be determined according to JIS K 6217-2:2001.

[0231] The dibutyl phthalate (DBP) oil absorption rate of the carbon black is preferably 5 ml / 100g or more, more preferably 70 ml / 100g or more, and even more preferably 90 ml / 100g or more. The DBP is also preferably 300 ml / 100g or less, more preferably 200 ml / 100g or less, even more preferably 160 ml / 100g or less, and particularly preferably 130 ml / 100g or less. When the DBP is within the above-specified range, beneficial effects are more likely to be achieved.

[0232] Here, the DBP of carbon black can be measured according to JIS-K 6217-4:2001.

[0233] Commercially available carbon black includes carbon black purchased from Asahi Carbon Co., Ltd., Cabot Japan Co., Ltd., Tokai Carbon Co., Ltd., Mitsubishi Chemical Co., Ltd., Lion Corporation, Shin-Nippon Chemical Carbon Co., Ltd., Columbia Carbon Materials Co., Ltd., etc.

[0234] The amount of carbon black is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, even more preferably 3 parts by mass or more, particularly preferably 5 parts by mass or more, but preferably 200 parts by mass or less, more preferably 150 parts by mass or less, even more preferably 120 parts by mass or less, and particularly preferably 80 parts by mass or less, when the amount is within the above-specified range, which tends to better achieve the beneficial effect.

[0235] The ratio of the amount of carbon black in parts by mass to the average primary particle size of the carbon black in nm, relative to 100 parts by mass of polymer component content (preferably relative to 100 parts by mass of rubber component content), is preferably 0.01 or more, more preferably 0.1 or more, even more preferably 1 or more, but preferably 2000 or less, more preferably 1500 or less, even more preferably 1000 or less, particularly preferably 10 or less, and most preferably 2 or less. When the ratio is within the range specified above, beneficial effects tend to be achieved better.

[0236] In this paper, the average primary particle size of carbon black can be determined by measuring the particle size of at least 400 primary carbon black particles observed in the field of view of a transmission or scanning electron microscope and averaging them.

[0237] The composition preferably contains sulfur.

[0238] Examples of sulfur include those commonly used in the rubber industry, such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersed sulfur, and soluble sulfur. These can be used alone or in combination of two or more.

[0239] Commercially available sulfur includes sulfur purchased from companies such as Tsurumi Chemical Industry Co., Ltd., Karuizawa Sulfur Co., Ltd., Shikoku Chemical Industry Co., Ltd., Flex Industries, Nippon Inkryu Co., Ltd., and Hosoi Chemical Industry Co., Ltd.

[0240] The amount of sulfur is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, relative to 100 parts by mass of polymer component content (preferably relative to 100 parts by mass of rubber component content). This amount is also preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and particularly preferably 5 parts by mass or less. When this amount is within the above-specified range, beneficial effects are more likely to be achieved.

[0241] The composition preferably contains a vulcanization accelerator.

[0242] Examples of vulcanization accelerators include thiazole vulcanization accelerators, such as 2-mercaptobenzothiazole and di-2-benzothiazole disulfide; thiuram vulcanization accelerators, such as tetramethylthiuram disulfide (TMTD), tetrabenzylthiuram disulfide (TBzTD), and tetra(2-ethylhexyl)thiuram disulfide (TOT-N); sulfenamide vulcanization accelerators, such as N-cyclohexyl-2-benzothiazole sulfenamide, N-tert-butyl-2-benzoazole sulfenamide, N-oxyethylene-2-benzimidazole sulfenamide, and N,N'-diisopropyl-2-benzothiphene sulfenamide; and guanidine vulcanization accelerators, such as diphenylguanidine, di-o-tolylguanidine, and o-tolyl biguanide. They can be used alone or in combination of two or more.

[0243] Commercially available vulcanization accelerators include those purchased from companies such as Kawaguchi Chemical Industry Co., Ltd., Ouchi New Chemical Industry Co., Ltd., and Rhein Chemical Company.

[0244] The amount of vulcanization accelerator is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, relative to 100 parts by mass of polymer component content (preferably relative to 100 parts by mass of rubber component content). This amount is also preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and particularly preferably 5 parts by mass or less. When this amount is within the above-specified range, beneficial effects are more likely to be achieved.

[0245] The composition preferably contains stearic acid.

[0246] Stearic acid that is commonly known can be used, including, for example, stearic acid purchased from companies such as Nippon Oil Co., Ltd., Kao Corporation, Fujifilm, and Koh Geny Co., Ltd., and Chiba Fatty Acid Co., Ltd.

[0247] The amount of stearic acid is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, relative to 100 parts by mass of polymer component content (preferably relative to 100 parts by mass of rubber component content). This amount is also preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and particularly preferably 5 parts by mass or less. When this amount is within the above-specified range, beneficial effects are more likely to be achieved.

[0248] The composition may contain zinc oxide.

[0249] Commonly known zinc oxides can be used, including, for example, those purchased from Mitsui Metal Mining Co., Ltd., Toho Co., Ltd., Hakusui Chemicals Co., Ltd., Seido Chemical Industry Co., Ltd., Sakai Chemical Industry Co., Ltd., etc.

[0250] The amount of zinc oxide is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, relative to 100 parts by mass of polymer component content (preferably relative to 100 parts by mass of rubber component content). This amount is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and particularly preferably 5 parts by mass or less. When this amount is within the above-specified range, beneficial effects are more likely to be achieved.

[0251] The composition may contain antioxidants.

[0252] Examples of antioxidants include naphthylamine-based antioxidants, such as phenyl-α-naphthylamine; diphenylamine-based antioxidants, such as octyl diphenylamine and 4,4′-bis(α,α′-dimethylbenzyl)diphenylamine; p-phenylenediamine-based antioxidants, such as N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, and N,N'-di-2-naphthyl-p-phenylenediamine; quinoline-based antioxidants, such as polymerized 2,2,4-trimethyl-1,2-dihydroquinoline; monophenol-based antioxidants, such as 2,6-di-tert-butyl-4-methylphenol and styrylated phenol; and bisphenol, triphenol, or polyphenol-based antioxidants, such as tetra[methylene-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate]methane. They can be used alone or in combination of two or more. Preferably, p-phenylenediamine-based antioxidants and quinoline-based antioxidants are used, with p-phenylenediamine-based antioxidants being more preferred.

[0253] Examples of commercially available antioxidants include those purchased from companies such as Seiko Chemical Co., Ltd., Sumitomo Chemical Co., Ltd., Ouchi Shinsei Chemical Co., Ltd., and Flextronics.

[0254] The amount of antioxidant is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, relative to 100 parts by mass of polymer component content (preferably relative to 100 parts by mass of rubber component content). This amount is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and particularly preferably 5 parts by mass or less. When this amount is within the above-specified range, beneficial effects are more likely to be achieved.

[0255] The composition may contain wax.

[0256] Any wax can be used, including petroleum waxes such as paraffin and microcrystalline wax; naturally occurring waxes such as plant and animal waxes; and synthetic waxes such as polymers of ethylene, propylene, or other similar monomers. They can be used alone or in combination of two or more.

[0257] Commercially available waxes include those purchased from companies such as Ouchi Shinshin Chemical Industry Co., Ltd., Nippon Seika Co., Ltd., and Seiko Chemical Co., Ltd.

[0258] The amount of wax is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, relative to 100 parts by mass of polymer component content (preferably relative to 100 parts by mass of rubber component content). This amount is also preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and particularly preferably 5 parts by mass or less. When this amount is within the above-specified range, beneficial effects are more likely to be achieved.

[0259] In addition to the components mentioned above, the composition may also contain additives commonly used in the tire industry, such as vulcanizing agents other than sulfur (e.g., organic crosslinking agents, organic peroxides), calcium carbonate, mica such as sericite, aluminum hydroxide, magnesium oxide, magnesium hydroxide, clay, talc, alumina, and titanium oxide. The amount of these components is preferably 0.1 parts by weight or more, but more preferably 200 parts by weight or less, relative to 100 parts by weight of polymer component content (preferably rubber component content).

[0260] The composition can be prepared, for example, by kneading the components using a rubber kneader (e.g., an open roller mill or a Banbury mixer) and then vulcanizing the kneaded mixture.

[0261] The kneading conditions are as follows. In the basic kneading step, which involves kneading additives other than the crosslinking agent (vulcanizing agent) and vulcanization accelerator, the kneading temperature is typically 100 to 180°C, preferably 120 to 170°C. In the final kneading step, which involves kneading the vulcanizing agent and vulcanization accelerator, the kneading temperature is typically below 120°C, preferably 80 to 110°C. The composition obtained after kneading the vulcanizing agent and vulcanization accelerator is then typically vulcanized, for example, by pressure vulcanization. The vulcanization temperature is typically 140 to 190°C, preferably 150 to 185°C.

[0262] The composition can be used (as a tire rubber composition) in tire components such as the tread (tread contact patch), sidewall, base tread, tread bottom layer, overlap, bead gusset, cushion pad rubber, carcass ply rubber, separator layer, bead, and inner liner, as well as the sidewall reinforcement layer of run-flat tires. Among other things, the composition can suitably be used in the tread. When the composition is used in the tread, it can be used only in the tread contact patch or only in the base tread, but preferably in both.

[0263] The tires of the present invention can be produced from the above-described composition by conventional methods. Specifically, the tires can be produced by extruding an uncured rubber composition containing the desired additives into the shape of tire components (particularly the tread (tread contact area)), then molding and assembling it with other tire components in a conventional manner on a tire forming machine to construct an uncured tire, and then heating and pressurizing the uncured tire in a vulcanizing machine.

[0264] The tire can be any type of tire, including pneumatic tires, solid tires, and airless tires. Pneumatic tires are preferred.

[0265] This tire can be appropriately used as a tire for passenger vehicles, large passenger vehicles, large SUVs, trucks and buses, or two-wheeled vehicles, or racing tires, winter tires (studless winter tires, snow tires, studded tires), all-season tires, run-flat tires, aircraft tires, mining tires, etc.

[0266] Example

[0267] The invention is described in detail with reference to, but not limited to, the embodiments.

[0268] Chemicals used in synthesis or polymerization are purified by conventional methods when necessary.

[0269] Furthermore, the methods used to evaluate the prepared polymers are summarized and described below.

[0270] (Measurement of weight-average molecular weight (Mw) and number-average molecular weight (Mn))

[0271] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer were determined by gel permeation chromatography (GPC) calibrated with polystyrene standards (GPC-8000 series from Tosoh Corporation, detector: differential refractometer, column: TSKGEL SUPERMULTIPORE HZ-M from Tosoh Corporation).

[0272] (Polymer structure identification)

[0273] The structure of the polymer was determined using a JNM-ECA series nuclear magnetic resonance spectrometer purchased from NEC Corporation. The cis content was determined by infrared absorption spectroscopy.

[0274] (Polymerization of resin A (α-methylstyrene resin, PAMS))

[0275] In a glass flask purged with inert gas, 1 g of aluminum chloride and 200 g of toluene were added. Then, 20 g of α-methylstyrene (AMS monomer) was added dropwise while maintaining the internal temperature between -50°C and -20°C. GPC analysis of the sample collected from the reaction solution revealed a weight-average molecular weight (Mw) of 2132, a number-average molecular weight (Mn) of 1132, and a molecular weight distribution of 1.9. The reaction solution was then stirred at room temperature. When the internal temperature reached above 0°C, 60 g of water was added to terminate the reaction. After separating and removing the aqueous layer, the process of adding water and separating was repeated until the pH of the aqueous layer reached above 4. Subsequently, the organic layer was obtained by separation, air-dried to evaporate the toluene, and then dried under reduced pressure at 80°C and below 10 Pa to constant weight to obtain resin A. The yield was almost 100%. GPC analysis showed a weight-average molecular weight (Mw) of 2045, a number-average molecular weight (Mn) of 980, and a molecular weight distribution of 2.1.

[0276] (Polymerization of resin B (ethyl vinyl ether resin (poly(ethyl vinyl ether), PEVE)))

[0277] 1 g of aluminum chloride and 200 g of toluene were added to a glass flask purged with an inert gas. Then, an ethyl vinyl ether solution (20.3 g of ethyl vinyl ether (EVE monomer), 100 g of toluene) was added dropwise to the flask while maintaining the internal temperature between -20°C and -5°C. GPC analysis of the sample collected from the reaction solution revealed a weight-average molecular weight (Mw) of 2201, a number-average molecular weight (Mn) of 1202, and a molecular weight distribution of 1.8. The reaction solution was stirred at room temperature, and when the internal temperature reached above 0°C, 60 g of water was added to terminate the reaction. After separating and removing the aqueous layer, the process of adding water and separating was repeated until the pH of the aqueous layer reached above 4. Subsequently, the organic layer was obtained by separation, air-dried to evaporate the toluene, and then dried under reduced pressure at 80°C and below 10 Pa to constant weight to obtain resin B. The yield was almost 100%. GPC analysis showed that its weight-average molecular weight (Mw) was 2205, number-average molecular weight (Mn) was 1110, and molecular weight distribution was 2.0.

[0278] (polymerization of resin C (poly(N-tert-butylacrylamide), PNTBAM))

[0279] 23.9 g of N-tert-butylacrylamide (NTBAM monomer) was added to a nitrogen-purged glass flask, followed by 200 mL of toluene. The mixture was stirred at room temperature for 30 minutes to obtain a homogeneous solution. Subsequently, 1.10 g of 2,2'-azobis(isobutyronitrile) (AIBN) was added to the solution, and the mixture was reacted under reflux for 3 hours. Toluene was then removed using a rotary evaporator, and the residue was dried under reduced pressure at 80 °C and below 10 Pa to constant weight to obtain resin C. The yield was almost 100%. GPC analysis showed a weight-average molecular weight (Mw) of 9721, a number-average molecular weight (Mn) of 3736, and a molecular weight distribution of 2.6.

[0280] (polymerization of resin D (poly(N-n-butylacrylamide), PNNBAM))

[0281] 23.9 g of N-n-butylacrylamide (NNBAM monomer) was added to a nitrogen-purged glass flask, followed by 200 mL of toluene. The mixture was stirred at room temperature for 30 minutes to obtain a homogeneous solution. Subsequently, 1.10 g of 2,2'-azobis(isobutyronitrile) (AIBN) was added to the solution, and the mixture was reacted under reflux for 3 hours. Toluene was then removed using a rotary evaporator, and the residue was dried under reduced pressure at 80 °C and below 10 Pa to constant weight to obtain resin D. The yield was almost 100%. GPC analysis showed a weight-average molecular weight (Mw) of 9521, a number-average molecular weight (Mn) of 3661, and a molecular weight distribution of 2.6.

[0282] (Confirming temperature-induced changes during interaction with antifreeze)

[0283] Each monomer or resin was incorporated into the antifreeze (a liquid composed of methanol and water, which can be prepared by mixing 9 times the volume of water with methanol at 25°C for 30 minutes) to a concentration of 1% by mass. The mixture was gradually heated from -20°C to +20°C while being stored at each temperature for 2 hours, and then the mixture was observed to be clear or cloudy. The results are shown in Table 1.

[0284] Table 1 Solubility of materials in antifreeze

[0285]

[0286]

[0287] Table 1 confirms the following.

[0288] Each monomer is soluble in antifreeze, and a clear solution can be obtained at all temperatures.

[0289] Resin A is insoluble in antifreeze at all temperatures.

[0290] Resin B yielded a clear solution at temperatures below 10°C, but at temperatures above 10°C, the solution gradually became cloudy, transforming into a dispersion containing insoluble matter. This indicates that the LCST of resin B (PEVE) is in the range of -10°C to +10°C.

[0291] Resin C forms a clear solution below 10°C, but gradually becomes cloudy and dispersed with insoluble matter above 10°C. This indicates that the LCST of resin C (PNTBAM) is in the range of -10°C to 10°C.

[0292] Resin D forms a clear solution below 10°C, but gradually becomes cloudy and dispersed with insoluble matter above 10°C. This indicates that the LCST of resin D (PNNBAM) is in the range of -10°C to 10°C.

[0293] The above results indicate that the group whose interaction with the antifreeze changes with temperature (preferably a group that exhibits a lower critical dissolution temperature in the antifreeze, more preferably a poly(alkyl vinyl ether) or a group of formula (II), even more preferably a group of formula (I) or a group of formula (II)) changes its interaction with the antifreeze with temperature. That is, since temperature changes may change hydrophilicity to change compatibility with other components in the composition, tire performance can be changed in response to temperature changes.

[0294] Furthermore, since the lower critical dissolution temperature of the functional group is -20°C to 20°C, tire performance can be modified within the required temperature range. Specifically, the plasticizer functions as a hydrophobic plasticizer at temperatures above the lower critical dissolution temperature of the functional group, and as a hydrophilic plasticizer at temperatures below the lower critical dissolution temperature. Therefore, it can be shown that the plasticizer can modify tire performance within this boundary temperature range, thereby allowing modification of tire performance within the required temperature range.

[0295] Synthesis of plasticizers containing groups whose interactions with antifreeze change with temperature.

[0296] (Polymerization of specific plasticizer A (α-methylstyrene-ethyl vinyl ether resin, PAMS-PEVE (resin B)))

[0297] In a glass flask purged with inert gas, 1 g of aluminum chloride and 200 g of toluene were added. Then, 20 g of α-methylstyrene was added dropwise while maintaining the internal temperature at -50 to -20 °C. GPC analysis of the sample collected from the reaction solution revealed a weight-average molecular weight (Mw) of 2165, a number-average molecular weight (Mn) of 1202, and a molecular weight distribution of 1.8. Next, an ethyl vinyl ether solution in toluene (20.3 g of ethyl vinyl ether monomer and 100 g of toluene) was added dropwise to the reaction solution while maintaining the internal temperature at -20 °C to -5 °C. GPC analysis of the sample collected from the reaction solution revealed a weight-average molecular weight (Mw) of 4231, a number-average molecular weight (Mn) of 2202, and a molecular weight distribution of 1.9. The reaction solution was stirred at room temperature. When the internal temperature reached above 0 °C, 60 g of water was added to terminate the reaction. After separating and removing the aqueous layer, the process of adding water and separating was repeated until the pH of the aqueous layer reached above 4. Subsequently, the organic layer was obtained by separation, air-dried to evaporate toluene, and then dried under reduced pressure at 80°C and below 10 Pa to constant weight, thereby obtaining specific plasticizer A. The yield was almost 100%. GPC analysis showed that its weight-average molecular weight (Mw) was 4231, number-average molecular weight (Mn) was 2202, and molecular weight distribution was 1.9.

[0298] (Polymerization of a specific plasticizer B (α-methylstyrene-N-tert-butylacrylamide resin, PAMS-PNTBAM (resin C)))

[0299] 20 g of α-methylstyrene was added to a nitrogen-purged glass flask, followed by 25 mL of toluene. The mixture was stirred at room temperature for 30 minutes to obtain a homogeneous solution. Subsequently, 1.10 g of 2,2'-azobis(isobutyronitrile) (AIBN) was added to the solution, and the mixture was refluxed for 3 hours. The reaction solution was cooled to 40 °C, and then 20 g of N-tert-butylacrylamide was added. The mixture was then refluxed for 3 hours. The toluene solvent was then removed from the reaction solution using a rotary evaporator, and the remaining dry solid was dried at 80 °C under reduced pressure below 0.1 Pa for 8 hours to obtain specific plasticizer B. The yield was almost 100%. GPC analysis showed a weight-average molecular weight (Mw) of 3265, a number-average molecular weight (Mn) of 1256, and a molecular weight distribution of 2.6.

[0300] (Polymerization of a specific plasticizer C (α-methylstyrene-N-n-butylacrylamide resin, PAMS-PNNBAM (resin D)))

[0301] 20 g of α-methylstyrene was added to a nitrogen-purged glass flask, followed by 25 mL of toluene. The mixture was stirred at room temperature for 30 minutes to obtain a homogeneous solution. Then, 1.10 g of 2,2'-azobis(isobutyronitrile) (AIBN) was added to the solution, and the mixture was refluxed for 3 hours. The reaction solution was cooled to 40 °C, and then 20 g of N-n-butylacrylamide was added. The mixture was then refluxed for 3 hours. The toluene solvent was then removed from the reaction solution using a rotary evaporator, and the remaining dry solids were dried at 80 °C under reduced pressure below 0.1 Pa for 8 hours to obtain the specified plasticizer C. The yield was almost 100%. GPC analysis showed a weight-average molecular weight (Mw) of 3374, a number-average molecular weight (Mn) of 1123, and a molecular weight distribution of 3.0.

[0302] (Polymerization of a specific plasticizer D (α-methylstyrene-ethyl vinyl ether resin, oily PAMS-PEVE (resin B)))

[0303] 1g of aluminum chloride and 200g of toluene were added to a glass flask purged with inert gas. Then, 5g of α-methylstyrene was added dropwise while maintaining the internal temperature at -50 to -20°C. GPC analysis of the sample collected from the reaction solution revealed a weight-average molecular weight (Mw) of 980, a number-average molecular weight (Mn) of 602, and a molecular weight distribution of 1.6. Next, an ethyl vinyl ether solution in toluene (35.0g of ethyl vinyl ether monomer and 100g of toluene) was added dropwise to the reaction solution while maintaining the internal temperature at -20°C to -5°C. GPC analysis of the sample collected from the reaction solution revealed a weight-average molecular weight (Mw) of 1127, a number-average molecular weight (Mn) of 701, and a molecular weight distribution of 1.6. The reaction solution was stirred at room temperature. When the internal temperature reached above 0°C, 60g of water was added to terminate the reaction. After separating and removing the aqueous layer, the process of adding water and separating was repeated until the pH of the aqueous layer reached above 4. Subsequently, the organic layer was obtained by separation, air-dried to evaporate toluene, and then dried under reduced pressure at 80°C and below 10 Pa to constant weight, thereby obtaining the specific plasticizer D. The yield was almost 100%. GPC analysis showed that its weight-average molecular weight (Mw) was 1042, number-average molecular weight (Mn) was 604, and molecular weight distribution was 1.7.

[0304] (Polymerization of a specific plasticizer E (liquid resin (polybutadiene) - PEVE (resin B)))

[0305] 1 g of aluminum chloride and 200 g of toluene were added to a glass flask purged with inert gas. Then, an ethyl vinyl ether solution in toluene (20.0 g ethyl vinyl ether monomer, 100 g toluene) was added dropwise to the flask while maintaining the internal temperature between -50 and -20 °C. GPC analysis of the sample collected from the reaction solution revealed a weight-average molecular weight (Mw) of 1129, a number-average molecular weight (Mn) of 988, and a molecular weight distribution of 1.6. Next, a maleic acid-modified BR solution in toluene (20.0 g maleic acid-modified BR, Ricon 130MA8, 100 g toluene) was added dropwise to the reaction solution while maintaining the internal temperature between -20 °C and -5 °C. GPC analysis of the sample collected from the reaction solution was performed. After confirming the appearance of a new peak at a higher molecular weight side of the maleic acid-modified BR material, the reaction solution was stirred at room temperature. When the internal temperature reached above 0 °C, 60 g of water was added to the reaction solution to terminate the reaction. After separating and removing the aqueous layer, the process of adding water and separating was repeated until the pH of the aqueous layer reached above 4. Subsequently, the organic layer was obtained by separation, air-dried to evaporate toluene, and then dried under reduced pressure at 80°C and below 10 Pa to constant weight, thereby obtaining the specific plasticizer E. The yield was almost 100%. GPC analysis showed that its weight-average molecular weight (Mw) was 3631, number-average molecular weight (Mn) was 2804, and molecular weight distribution was 1.3.

[0306] (Polymerization of a specific plasticizer F (polystyrene-ethyl vinyl ether resin, PS-PEVE (resin B)))

[0307] In a glass flask purged with inert gas, 1 g of aluminum chloride and 200 g of toluene were added. Then, 20 g of styrene was added dropwise to the flask while maintaining the internal temperature between 0 and 20 °C. GPC analysis of the sample collected from the reaction solution revealed a weight-average molecular weight (Mw) of 1565, a number-average molecular weight (Mn) of 1122, and a molecular weight distribution of 1.4. Next, a solution of ethyl vinyl ether in toluene (20.3 g of ethyl vinyl ether monomer and 100 g of toluene) was added dropwise to the reaction solution while maintaining the internal temperature between 0 and 20 °C. GPC analysis of the sample collected from the reaction solution revealed a weight-average molecular weight (Mw) of 3231, a number-average molecular weight (Mn) of 2302, and a molecular weight distribution of 1.4. The reaction solution was stirred at room temperature. When the internal temperature reached above 20 °C, 60 g of water was added to terminate the reaction. After separating and removing the aqueous layer, the process of adding water and separating was repeated until the pH of the aqueous layer reached above 4. Subsequently, the organic layer was obtained by separation, air-dried to evaporate toluene, and then dried under reduced pressure at 80°C and below 10 Pa to constant weight, thereby obtaining the specific plasticizer F. The yield was almost 100%. GPC analysis showed that its weight-average molecular weight (Mw) was 3331, number-average molecular weight (Mn) was 2342, and molecular weight distribution was 1.4.

[0308] (Polymerization of a specific plasticizer G (polyterpene-ethyl vinyl ether resin, PTR-PEVE (resin B)))

[0309] 1 g of aluminum chloride and 200 g of toluene were added to a glass flask purged with an inert gas. Then, 20 g of β-pinene was added dropwise to the flask while maintaining the internal temperature between 0 and 20 °C. GPC analysis of the sample collected from the reaction solution revealed a weight-average molecular weight (Mw) of 1065, a number-average molecular weight (Mn) of 802, and a molecular weight distribution of 1.3. Next, a solution of ethyl vinyl ether in toluene (20.3 g of ethyl vinyl ether monomer and 100 g of toluene) was added dropwise to the reaction solution while maintaining the internal temperature between 0 and 20 °C. GPC analysis of the sample collected from the reaction solution revealed a weight-average molecular weight (Mw) of 2252, a number-average molecular weight (Mn) of 1165, and a molecular weight distribution of 1.9. The reaction solution was stirred at room temperature. When the internal temperature reached above 20 °C, 60 g of water was added to terminate the reaction. After separating and removing the aqueous layer, the process of adding water and separating was repeated until the pH of the aqueous layer reached above 4. Subsequently, the organic layer was obtained by separation, air-dried to evaporate toluene, and then dried under reduced pressure at 80°C and below 10 Pa to constant weight, thereby obtaining the specific plasticizer G. The yield was almost 100%. GPC analysis showed that its weight-average molecular weight (Mw) was 2382, the number-average molecular weight (Mn) was 1342, and the molecular weight distribution was 1.8.

[0310] The specific plasticizers A to G prepared above are all plasticizers containing groups whose interaction with the antifreeze changes with temperature, and their lower critical dissolution temperature is -20℃ to 20℃.

[0311] Synthesis of Polymers (Rubber Components)

[0312] (Polymerization of polymer A)

[0313] 1500 mL of n-hexane, 25 g of styrene, 75 g of 1,3-butadiene, 0.2 mmol of tetramethylethylenediamine, and 0.24 mmol of n-butyllithium were placed in a heat-resistant container thoroughly purged with nitrogen, and then stirred at 0 °C for 48 hours. The reaction was then terminated by adding an alcohol. Next, 24 mL of a 1 mmol / L BHT ethanol solution was added to the reaction solution. A 10 mL fraction of the polymerization solution was collected, precipitated with 40 mL of ethanol, and then dried to obtain polymer A. The copolymer obtained thus had a weight-average molecular weight of 460,000, a styrene content of 25% by mass, and a yield of 99%.

[0314] (Polymerization of polymer B)

[0315] Preparation of catalyst solution B

[0316] In a dry, nitrogen-purged 1L pressure-resistant stainless steel container, add 350 mL of cyclohexane and 35 g of 1,3-butadiene monomer. Add 54 mL of a 20% (v / v) Nd:cyclohexane tert-tert-carbonate solution, then add 130 mL of PMAO solution dissolved in toluene, and stir for 30 minutes. Next, add 30 mL of 1M DAIBAH solution dissolved in hexane, and stir for 30 minutes. Subsequently, add 15 mL of 1M 2-chloro-2-methylpropane solution in cyclohexane, and stir for 30 minutes to obtain catalyst solution B.

[0317] Polymerization of polymer B

[0318] In a dry, nitrogen-purged 3L pressure-resistant stainless steel container, add 2000 mL of cyclohexane and 100 g of 1,3-butadiene, then add 10 mL of a 1 mol / L TIBA solution in n-hexane, and stir for 5 minutes. After confirming the solution is clear, add 30 mL of catalyst solution B, and carry out the polymerization reaction at 80 °C for 3 hours. After 3 hours, add 50 mL of a 1M isopropanol solution in THF as a reaction terminator to terminate the reaction. Collect 10 mL of the polymerization solution, precipitate with 40 mL of ethanol, and then dry to obtain polymer B.

[0319] The polymer has a weight-average molecular weight of 800,000, a cis content of 98% by mass, and a yield of 99%.

[0320] (Production of hydrogenated SBR)

[0321] Hexane, styrene, 1,3-butadiene, N,N,N',N'-tetramethylethylenediamine (TMEDA), and n-butyllithium were charged into a heat-resistant reaction vessel thoroughly purified with nitrogen, and then stirred at 50°C for 5 hours to carry out the polymerization reaction. Subsequently, the reaction solution was stirred for 20 minutes while hydrogen was supplied at a gauge pressure of 0.4 MPa to allow unreacted polymer-terminated lithium to react with hydrogen to form lithium hydride. Hydrogenation was carried out using a titanium dichloride-based catalyst at a hydrogen supply pressure of 0.7 MPa and a reaction temperature of 90°C. Once the accumulated amount of absorbed hydrogen reached the amount corresponding to the target degree of hydrogenation, the reaction temperature was lowered to room temperature, and the hydrogen pressure was restored to atmospheric pressure. The reaction solution was then evacuated from the reaction vessel and introduced into water with stirring. The solvent was then removed by stripping to obtain hydrogenated SBR.

[0322] The chemicals used in the examples and comparative examples are listed below.

[0323] NR: TSR20 (Natural Rubber)

[0324] SBR: Polymer A mentioned above

[0325] Hydrogenated SBR: The above hydrogenated SBR (conjugated diene units: 3.3 mol%, non-conjugated olefin units: 88.2 mol%, aromatic vinyl units: 8.5 mol% (styrene content: 25% by mass), Mw: 45000)

[0326] BR: The above polymer B

[0327] Resins A to D: The above-mentioned resins A to D

[0328] Specific plasticizers A to G: The above-mentioned specific plasticizers A to G

[0329] Carbon black: N110 (N2SA: 144m) 2 / g, DBP: 115ml / 100g, average primary particle size: 18nm), purchased from Cabot Corporation, Japan.

[0330] Silica: ULTRASIL VN3 (N2SA: 175m) 2 / g, average primary particle size: 16nm), purchased from Evonik Degussa.

[0331] Silane coupling agent: Si69 (bis(3-triethoxysilylpropyl)tetrasulfide), purchased from Evonik Degussa.

[0332] Antioxidant: NOCRAC 6C (N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine), purchased from Ouchi Shinsei Chemical Co., Ltd.

[0333] Stearic acid: purchased from Nippon Oil Co., Ltd.

[0334] Zinc oxide: Zinc oxide #1, purchased from Mitsui Metals & Mining Co., Ltd.

[0335] Sulfur: Powdered sulfur, purchased from Tsurumi Chemical Industry Co., Ltd.

[0336] Vulcanization accelerator (1): NOCCELER CZ (N-cyclohexyl-2-benzothiazole sulfenamide), purchased from Ouchi Shinshin Chemical Co., Ltd.

[0337] Vulcanization accelerator (2): NOCCELER D (1,3-diphenylguanidine), purchased from Ouchi Shinsei Chemical Co., Ltd.

[0338] (Examples and Comparative Examples)

[0339] According to the compounding formulation shown in Table 2, the chemicals, excluding sulfur and vulcanization accelerator, were kneaded for 5 minutes at 150°C using a 1.77L Banbury mixer (Kobe Steel Co., Ltd.) to obtain a kneaded mixture. Then, sulfur and vulcanization accelerator were added to the kneaded mixture and kneaded for 5 minutes in an open roller mill at 80°C to obtain an unvulcanized rubber composition.

[0340] The uncured rubber composition was subjected to pressure vulcanization at 170°C for 15 minutes to obtain a vulcanized rubber composition.

[0341] The vulcanized rubber composition prepared above was evaluated as follows. Table 2 shows the results.

[0342] (Fuel Economy)

[0343] Using a spectrometer purchased from Uejima Manufacturing Co., Ltd., the tanδ of each vulcanized rubber composition was measured at a dynamic strain amplitude of 1%, a frequency of 10 Hz, and a temperature of 50°C. The reciprocal of tanδ was then expressed as an exponent (=100) relative to Comparative Example 1. A higher exponent indicates lower rolling resistance and better fuel economy.

[0344] (Wet grip performance)

[0345] Wet grip performance was evaluated using a flat belt friction testing machine (FR5010 model) purchased from Uejima Manufacturing Co., Ltd. At a speed of 20 km / h, a load of 4 kgf, and a road surface temperature of 20°C, the slip ratio of the specimens on the road surface was varied from 0% to 70%. Cylindrical rubber samples (width: 20 mm, diameter: 100 mm) prepared for each vulcanized rubber composition were tested, and the maximum coefficient of friction detected was read and expressed as an exponent (=100) relative to Comparative Example 1. A higher exponent indicates a higher maximum coefficient of friction and better wet grip.

[0346] The sum of the two indicators, fuel economy and wet grip performance, indicates the overall performance in terms of both.

[0347]

[0348]

[0349] Table 2 shows compositions comprising plasticizers for resins and / or elastomers, wherein the plasticizer contains groups that change their interaction with the antifreeze with temperature, and the lower critical dissolution temperature of these groups is -20°C to 20°C. These compositions can modify tire performance within the temperature range required by the tire and can also be used to prepare tire compositions.

[0350] Exemplary embodiments of the present invention include:

[0351] Embodiment 1. A plasticizer, used in at least one of a resin and an elastomer,

[0352] The plasticizer contains groups that alter their interaction with the antifreeze as temperature changes.

[0353] The lower critical dissolution temperature of this group is -20℃ to 20℃.

[0354] Implementation Method 2. The plasticizer according to Implementation Method 1,

[0355] The plasticizer is an oil, ester, liquid resin, or solid resin.

[0356] Implementation Method 3. The plasticizer according to Implementation Method 1,

[0357] The plasticizer is a liquid resin or a solid resin.

[0358] Embodiment 4. The plasticizer according to any one of Embodiments 1 to 3,

[0359] The lower critical dissolution temperature of the group is -20°C to 10°C.

[0360] Embodiment 5. The plasticizer according to any one of Embodiments 1 to 4,

[0361] Wherein, the group is a group represented by formula (I) or a group represented by formula (II):

[0362] [Chemistry 7]

[0363]

[0364] In the formula, n represents an integer from 1 to 1000; R 1 R 2 and R 3 Each can independently represent a hydrogen atom or a hydrocarbon group.

[0365] [Chemistry 8]

[0366]

[0367] In the formula, n represents an integer from 1 to 1000; R 4 Indicates n-butyl or tert-butyl; R 5 It represents a hydrogen atom or a hydrocarbon group.

[0368] Embodiment 6. The plasticizer according to any one of Embodiments 1 to 5,

[0369] Wherein, the group is poly(ethyl vinyl ether), poly(N-tert-butylacrylamide), or poly(N-n-butylacrylamide).

[0370] Embodiment 7. A composition comprising the plasticizer described in any one of Embodiments 1 to 6.

[0371] Embodiment 8. The composition according to Embodiment 7,

[0372] The composition contains at least one type of rubber.

[0373] Embodiment 9. The composition according to Embodiment 8,

[0374] The rubber comprises a multi-component copolymer, which includes conjugated diene units, non-conjugated olefin units, and aromatic vinyl units.

[0375] Embodiment 10. The composition according to Embodiment 8 or 9,

[0376] The composition comprises silicon dioxide, and

[0377] The ratio of the amount of silica in the composition by mass to the average primary particle size of silica in nm, relative to 100 parts by mass of rubber component, is 1 to 1000.

[0378] Embodiment 11. The composition according to any one of Embodiments 8 to 10,

[0379] The composition comprises carbon black.

[0380] The ratio of the amount of carbon black in the composition, by mass, to the average primary particle size of the carbon black, in nm, is 1 to 1000, relative to 100 parts by mass of rubber component content.

[0381] Embodiment 12. The composition according to any one of Embodiments 7 to 11,

[0382] The composition is used in tire treads.

[0383] Embodiment 13. A tire comprising a tire component formed of any one of Embodiments 7 to 12.

[0384] Implementation Method 14. The tire according to Implementation Method 13,

[0385] The tire component is the tire tread.

Claims

1. A composition comprising a plasticizer for at least one of a resin and an elastomer, characterized in that, The plasticizer is grafted with groups that alter their interaction with the antifreeze as temperature changes. The antifreeze is a liquid composed of methanol and water. The group is a group represented by formula (I) or a group represented by formula (II): [Chemistry 1] In the formula, n represents an integer from 1 to 1000; R 1 R 2 and R 3 Each can independently represent a hydrogen atom or a hydrocarbon group. [Chemistry 2] In the formula, n represents an integer from 1 to 1000; R 4 Indicates n-butyl or tert-butyl; R 5 Represents a hydrogen atom or a hydrocarbon group; The lower critical dissolution temperature of the group is -20°C to 20°C; Wherein, the plasticizer is an oil-based plasticizer, an ester-based plasticizer, a liquid resin, or a solid resin; and The composition contains at least one type of rubber.

2. The composition according to claim 1, in, The plasticizer is a liquid resin or a solid resin.

3. The composition according to claim 1 or 2, in, The lower critical dissolution temperature of the group is -20°C to 10°C.

4. The composition according to claim 1 or 2, in, The group is poly(ethyl vinyl ether), poly(N-tert-butylacrylamide), or poly(N-n-butylacrylamide).

5. The composition according to claim 1 or 2, in, The rubber comprises a multi-component copolymer, which includes conjugated diene units, non-conjugated olefin units, and aromatic vinyl units.

6. The composition according to claim 1 or 2, in, The composition contains silicon dioxide. The ratio of the amount of silica in the composition by mass to the average primary particle size of silica in nm, relative to 100 parts by mass of rubber component, is 1 to 1000.

7. The composition according to claim 1 or 2, in, The composition contains carbon black. The ratio of the amount of carbon black in the composition, by mass, to the average primary particle size of the carbon black, in nm, is 1 to 1000, relative to 100 parts by mass of rubber component content.

8. The composition according to claim 1 or 2, in, The composition is used for tire treads.

9. A tire comprising a tire component formed of the composition of any one of claims 1 to 8.

10. The tire according to claim 9, in, The tire component is the tread.

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