JP6236232B2 - Composition of conjugated diene polymer - Google Patents

Description

  The present invention relates to a composition comprising a conjugated diene polymer and a stabilizer.

  Conjugated diene polymers make use of excellent properties such as transparency and belt impact properties, and can be used alone or mixed with other resins or alloyed to produce food packaging materials such as sheets, films, and trays, automobile bodies, tires, and home appliances. Or, it is used for a wide range of applications such as the housing of OA equipment. Although the conjugated diene polymer is excellent in the above properties, it has a problem in thermal stability. In order to cause yellowing due to thermal deterioration in the process of melting and heating at the time of molding, a heat stabilizer is added after polymerization. Measures are taken.

  For example, in Patent Document 1, by adding a thermal stabilizer such as phenol, phosphorus or amine to a polymer solution after polymerizing a conjugated diene and / or aromatic vinyl, the polymer is recovered, It is disclosed that the color tone and transparency of the polymer are improved.

  In Patent Document 2, in the step of obtaining a polymer from the polymer solution, a heat stabilizer such as 2,4bis [(octylthio) methyl] -o-cresol is added to the polymer solution, so that the gel is reduced and the color tone is reduced. It is disclosed that excellent polymer pellets can be obtained.

Japanese Patent Laid-Open No. 9-255716 JP-A-11-171949

  However, even the conjugated diene polymer obtained by the techniques disclosed in Patent Documents 1 and 2 above does not sufficiently satisfy the required level of higher thermal stability from the market, and further improvement in thermal stability. Is needed.

  Therefore, the present invention provides a composition containing a conjugated diene polymer, which is excellent in thermal stability and suppresses yellowing even when used in molding and heating or in a high-temperature environment. With the goal.

As a result of studying suppression of yellowing when heating a conjugated diene polymer, the addition of a compound having a specific structure improves the thermal stability of the conjugated diene polymer and is effective in suppressing yellowing during heating. As a result, the present invention was reached.
[1]
(A) 100 parts by mass of a conjugated diene polymer;
(B) 5 × 10 ^{−4 to} 100 × 10 ⁻⁴ parts by mass of a compound represented by the following formula (1),
A composition comprising :
(In formula (1), _one of R _{1 to} R ₆ is an alkyl group having 1 to 6 carbon atoms, one is a hydrogen atom, two are thioether groups, and two are hydroxyl groups. is there.)
The component (B) is a compound represented by the following formula (1-1) and / or represented by the following formula (1-2).
A composition which is a compound to be prepared.
(In the formula (1-1), R ₁₆ is an alkyl group having 1 to 6 carbon atoms, and R ₁₇ and R ₁₈ are
It is an alkyl group having 4 to 12 carbon atoms. )
(In the formula (1-2), R ₁₉ is an alkyl group having 1 to 6 carbon atoms, and R ₂₀ and R ₂₁ are
It is an alkyl group having 4 to 12 carbon atoms. )
[2]
(C) Compound 0 represented by the following formula (2) with respect to 100 parts by mass of component (A)
. It is a composition as described in [1] containing 01-1 mass part ,
(In formula (2), one of R _{7 to} R ₁₂ is an alkyl group having 1 to 6 carbon atoms, two are hydrogen atoms, two are thioether groups, and one is a hydroxyl group. is there.)
The composition according to [1], wherein the component (C) is a compound represented by the following formula (2-1):
.
(In the formula (2-1), R ₁₃ is an alkyl group having 1 to 6 carbon atoms, and R ₁₄ and R ₁₅ are
It is an alkyl group having 4 to 12 carbon atoms. )

  The composition of the present invention is excellent in thermal stability even during heating during molding and use in a high temperature environment, and yellowing can be suppressed.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.

  In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.

≪Composition≫
The composition of the present embodiment comprises (A) 100 parts by mass of a conjugated diene polymer (hereinafter also referred to as “component (A)”) and (B) a compound represented by the following formula (1) (hereinafter referred to as “(B ) Component ”). 5 × 10 ^{−4 to} 100 × 10 ⁻⁴ parts by mass.
(In formula (1), _one of R _{1 to} R ₆ is an alkyl group having 1 to 6 carbon atoms, one is a hydrogen atom, two are thioether groups, and two are hydroxyl groups. is there.)

<(A) component>
The conjugated diene polymer used in the present embodiment refers to a polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound. The polymer of the conjugated diene compound and the copolymer of the conjugated diene compound and the aromatic vinyl compound may contain other monomers copolymerizable with the conjugated diene compound.

  The conjugated diene compound is not particularly limited as long as it is a polymerizable monomer. For example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl- 1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene and the like can be mentioned. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of industrial availability. These may be used alone or in combination of two or more.

  The aromatic vinyl compound is not particularly limited as long as it is a monomer copolymerizable with a conjugated diene compound. For example, styrene, m or p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene. , Diphenylethylene, divinylbenzene and the like. Among these, styrene is preferable from the viewpoint of industrial availability. These may be used alone or in combination of two or more.

  The other monomer copolymerizable with the conjugated diene compound is not particularly limited, and examples thereof include methacrylic acid ester, acrylic acid ester, acrylonitrile, acrylamide, cyclohexene, cyclohexadiene, and cyclopentene. These may be used alone or in combination of two or more.

  If the conjugated diene compound contains allenes, acetylenes or the like as impurities, there is a risk of inhibiting the modification reaction described later. Therefore, the total content concentration (mass) of these impurities in the conjugated diene compound is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.

  The allenes are not particularly limited, and examples thereof include propadiene and 1,2-butadiene. Although it does not specifically limit as acetylene, For example, ethyl acetylene, vinyl acetylene, etc. are mentioned.

  When the conjugated diene polymer is a copolymer, it may be a random copolymer or a block copolymer.

  Although it does not specifically limit as a random copolymer, For example, a butadiene-isoprene random copolymer, a butadiene-styrene random copolymer, an isoprene-styrene random copolymer, a butadiene-isoprene-styrene random copolymer, etc. are mentioned. . The composition distribution of each monomer in the copolymer chain is not particularly limited, and examples thereof include a completely random copolymer close to a statistical random composition, and a tapered (gradient) random copolymer having a gradient in composition distribution. It is done. The bonding mode of the conjugated diene, that is, the composition such as 1,4-bond or 1,2-bond may be uniform or different depending on the molecular chain.

  Although it does not specifically limit as a block copolymer, For example, the 2 type block copolymer which consists of 2 blocks, the 3 type 3 block copolymer which consists of 3, 4 type 4 block copolymer etc. are mentioned It is done. Here, a block composed of an aromatic vinyl compound such as styrene is represented by S, and a block composed of a conjugated diene compound such as butadiene or isoprene and / or a block composed of a copolymer of an aromatic vinyl compound and a conjugated diene compound is represented by B. If it represents, it will not specifically limit as a block copolymer, For example, a S-B2 type block copolymer, a S-B-S3 type block copolymer, a S-B-S-B4 type block copolymer etc. Can be mentioned.

  In the above equation, the boundaries of each block need not be clearly distinguished. For example, when the block B is a copolymer of an aromatic vinyl compound and a conjugated diene compound, the aromatic vinyl compound in the block B may be distributed uniformly or in a tapered shape. Further, a plurality of portions where the aromatic vinyl compound is uniformly distributed and / or portions where the aromatic vinyl compound is distributed in a tapered shape may coexist in the block B. Furthermore, a plurality of segments having different aromatic vinyl compound contents may coexist in the block B. When a plurality of blocks S and blocks B are present in the copolymer, the structures such as molecular weight and composition thereof may be the same or different.

<Production method of component (A)>
The component (A) used in the present embodiment is not particularly limited, but for example, by anionic polymerization of the above conjugated diene compound and any other conjugated diene compound that can be polymerized with a polymerization initiator. Can be obtained.

  The organic alkali metal compound used as the polymerization initiator is not particularly limited, but an organic lithium compound is preferable. Although it does not specifically limit as an organic lithium compound, For example, a low molecular compound and the solubilized oligomeric organic lithium compound are mentioned. In addition, the organic lithium compound represented by the bonding mode between the organic group and lithium is not particularly limited. For example, the organic lithium compound having a carbon-lithium bond, the organic lithium compound having a nitrogen-lithium bond, and a tin-lithium bond. And organolithium compounds having

  The organic lithium compound having a carbon-lithium bond is not particularly limited, and examples thereof include n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, benzyllithium, phenyllithium, and stilbenelithium. .

  The organic lithium compound having a nitrogen-lithium bond is not particularly limited, and examples thereof include lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium di-n-hexylamide, lithium diisopropylamide, lithium hexamethyleneimide, and lithium pyrrolidide. Lithium piperidide, lithium heptamethyleneimide, lithium morpholide and the like.

  As the organolithium compound, not only the monoorganolithium compound described above but also a polyfunctional organolithium compound can be used, or polymerization can be performed in combination with the monoorganolithium compound.

  Although it does not specifically limit as a polyfunctional organolithium compound, For example, the reaction product of 1, 4- dilithiobutane, sec-butyllithium and diisopropenylbenzene, 1,3,5-trilithiobenzene, n-butyllithium and 1 , 3-butadiene and a reaction product of divinylbenzene, a reaction product of n-butyllithium and a polyacetylene compound, and the like. Furthermore, organic alkali metal compounds disclosed in US Pat. No. 5,708,092, British Patent 2,241,239, US Pat. No. 5,527,753, etc. are also used. be able to.

  As the organic lithium compound, n-butyllithium and sec-butyllithium are preferable from the viewpoint of industrial availability and ease of control of the polymerization reaction.

  The organic lithium compound may be used as a mixture of not only one type but also two or more types.

  Although it does not specifically limit as another organic alkali metal compound, For example, an organic sodium compound, an organic potassium compound, an organic rubidium compound, an organic cesium compound etc. are mentioned. Specific examples include, but are not limited to, sodium naphthalene, potassium naphthalene, and the like. In addition, alkoxides such as lithium, sodium, and potassium, sulfonates, carbonates, amides, and the like can be given.

  The organic alkali metal compound described above may be used in combination with an organic alkaline earth metal compound or other organic metal compound.

  Although it does not specifically limit as an organic alkaline-earth metal compound used as a polymerization initiator, For example, an organic magnesium compound, an organic calcium compound, an organic strontium compound etc. are mentioned. Further, alkaline earth metal alkoxides, sulfonates, carbonates, amides and other compounds may be used. These organic alkaline earth metal compounds may be used in combination with alkali metal compounds or other organic metal compounds.

  Conjugated diene weight obtained by anionic polymerization (copolymerization) of a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound using the above-described organic alkali metal compound and / or organic alkaline earth metal compound as a polymerization initiator. The coalescence has a polymerization active end. In particular, the conjugated diene polymer is more preferably a conjugated diene polymer having a polymerization active terminal obtained by a growth reaction by living anion polymerization. By performing a modification reaction using such a conjugated diene polymer having a polymerization active terminal, a modified conjugated diene polymer having a high modification rate can be obtained. The component (A) used in the present embodiment may be a modified conjugated diene polymer.

  The polymerization process may be any of continuous, batch, and semi-batch processes, but the continuous process is preferred because the resulting conjugated diene polymer has good wear resistance when used as a tire raw material. In a continuous process, one or more connected reactors can be used, but a continuous polymerization process using two or more connected reactors can reduce the molecular weight distribution of the resulting polymer. It is also preferable from the viewpoint of controlling the molecular weight distribution. The reactor is not particularly limited, and for example, a tank type with a stirrer, a tube type, or the like can be used.

  The polymerization reaction for obtaining the conjugated diene polymer is preferably performed in a solvent. The solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specific examples include, but are not limited to, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane; benzene, toluene, and xylene And hydrocarbons composed of aromatic hydrocarbons and mixtures thereof.

  Treatment of allenes and acetylenes, which are impurities in the conjugated diene compound, with an organometallic compound prior to the polymerization reaction tends to yield a conjugated diene polymer having a high concentration of active ends, This is preferable because a high modification rate tends to be achieved.

  In the polymerization reaction for obtaining the conjugated diene polymer, a polar compound may be added. The polar compound can be used for randomly copolymerizing an aromatic vinyl compound with a conjugated diene compound, and can also be used as a vinylating agent for controlling the microstructure of the conjugated diene portion. Polar compounds are also effective in improving the polymerization rate.

  Although it does not specifically limit as a polar compound, For example, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2, 2-bis (2-oxolanyl) propane, etc. Ethers; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; potassium-t-amylate, potassium-t-butylate, sodium-t-butylate, sodium amylate, etc. Alkali metal alkoxide compounds of the above; phosphine compounds such as triphenylphosphine can be used. These polar compounds may be used alone or in combination of two or more.

  The usage-amount of a polar compound is not specifically limited, It can select according to the objective etc. Usually, it is preferable that it is 0.01-100 mol with respect to 1 mol of polymerization initiators. An appropriate amount of such a polar compound (vinylating agent) can be used as a regulator of the microstructure of the polymer conjugated diene moiety depending on the desired vinyl bond amount.

  Many polar compounds simultaneously have an effective randomizing effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound, and can be used as an adjustment of the distribution of the aromatic vinyl compound and an adjuster of the styrene block amount. As a method for randomizing the conjugated diene compound and the aromatic vinyl compound, for example, as described in JP-A-59-140221, a part of 1,3-butadiene is intermittently produced during the copolymerization. You may use the method of adding to.

  The polymerization temperature for obtaining the conjugated diene polymer is not particularly limited as long as the polymerization proceeds. However, from the viewpoint of productivity, the polymerization temperature is preferably 0 ° C. or higher. From the viewpoint of ensuring a sufficient amount of reaction, it is preferably 120 ° C. or lower. Further, from the viewpoint of preventing cold flow of the conjugated diene polymer, a polyfunctional aromatic vinyl compound such as divinylbenzene for controlling branching may be used.

  For example, a modified conjugated diene polymer can be obtained by preparing a conjugated diene polymer having a polymerization active end by the above-described method and then reacting the polymerization active end with a modifier having an alkoxysilyl group. it can.

Although it does not specifically limit as a modifier | denaturant which has an alkoxy silyl group, For example, the compound represented by following General formula (6) is mentioned.

In formula (6), X is Cl, Br or I, R ²² and R ²³ are each independently an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 6 carbon atoms or a vinyl group, m Is an integer of 0-4, n is an integer of 0-4, and m + n is 2-4. In addition, the group represented by R ²² and R ²³ may be substituted. Further, when there are a plurality of X, they may be the same or different. Further, when there are a plurality of R ²² and R ²³ as well, they may be the same or different.

  Specific examples of the modifying agent having an alkoxysilyl group are not particularly limited. Butoxy) ethylsilane, tri (2-methylbutoxy) vinylsilane, triphenoxyphenylsilane, tetraphenoxysilane, tetraethoxysilane, tetramethoxysilane, tetrakis (2-ethylhexyloxy) silane, phenoxydivinylchlorosilane, methoxydiethylchlorosilane, diphenoxymethyl Chlorosilane, diphenoxyphenyliodosilane, diethoxymethylchlorosilane, dimethoxyethylchlorosilane, triethoxychlorosilane Triphenoxychlorosilane, tris (2-ethylhexyloxy) chlorosilane, phenoxymethyldichlorosilane, methoxyethyldichlorosilane, ethoxymethyldichlorosilane, phenoxyphenyldiiodosilane, phenoxydichlorosilane, dimethoxydichlorosilane, bis (2-methylbutoxy) dibromo Silane etc. are mentioned.

  Furthermore, among the modifiers having an alkoxysilyl group, it is preferable to use a compound having an N atom and a plurality of alkoxysilyl groups in the molecule.

  The compound having an N atom and a plurality of alkoxysilyl groups in the molecule is not particularly limited. For example, 1- [3- (trialkoxysilyl) -propyl] -4-alkylpiperazine, 1- [3- (Alkyldialkoxysilyl) -propyl] -4-alkylpiperazine, 1- [3- (trialkoxysilyl) -propyl] -3-alkylimidazolidine, 1- [3- (alkyldialkoxysilyl) -propyl]- 3-alkylimidazolidine, 1- [3- (trialkoxysilyl) -propyl] -3-alkylhexahydropyrimidine, 1- [3- (alkyldialkoxysilyl) -propyl] -3-alkylhexahydropyrimidine, 3 -[3- (trialkoxysilyl) -propyl] -1-alkyl-1,2,3,4-tetrahydropyrimidine, 3- [ - (alkyldialkoxysilyl) - propyl] -1-alkyl-1,2,3,4-tetrahydropyrimidine and the like. Although it does not specifically limit as a specific example of such a compound, For example, 1- [3- (triethoxysilyl) -propyl] -4-methylpiperazine, 1- [3- (diethoxyethylsilyl) -propyl] -4-methylpiperazine, 1- [3- (trimethoxysilyl) -propyl] -3-methylimidazolidine, 1- [3- (diethoxyethylsilyl) -propyl] -3-ethylimidazolidine, 1- [ 3- (triethoxysilyl) -propyl] -3-methylhexahydropyrimidine, 1- [3- (dimethoxymethylsilyl) -propyl] -3-methylhexahydropyrimidine, 3- [3- (tributoxysilyl)- Propyl] -1-methyl-1,2,3,4-tetrahydropyrimidine, 3- [3- (dimethoxymethylsilyl) -propyl] -1-ethyl-1,2,3,4 -Tetrahydropyrimidine, 1- (2-ethoxyethyl) -3- [3- (trimethoxysilyl) -propyl] -imidazolidine, (2- {3- [3- (trimethoxysilyl) -propyl] -tetrahydropyrimidine -1-yl} -ethyl) dimethylamine and the like.

  In addition, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1 -Aza-2-silacyclopentane, 2,2-dimethoxy-1- (4-trimethoxysilylbutyl) -1-aza-2-silacyclohexane, 2,2-dimethoxy-1- (5-trimethoxysilylpentyl) ) -1-aza-2-silacycloheptane, 2,2-dimethoxy-1- (3-dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3- Diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2-methyl-1- (3-trimethoxysilylpropyl) -1-aza-2- Lacyclopentane, 2-ethoxy, 2-ethyl-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2-methyl-1- (3-dimethoxymethylsilylpropyl) ) -1-aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane, and the like.

  Among these, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2 is used from the viewpoint of the reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica. -Silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 1- [3- (triethoxysilyl) -propyl] -4-methylpiperazine Is preferred.

  After performing the modification reaction, a deactivator, a neutralizing agent and the like may be added to the copolymer solution as necessary. Although it does not specifically limit as a quencher, For example, alcohol; alcohol, such as water; methanol, ethanol, isopropanol, etc. are mentioned. The neutralizing agent is not particularly limited, and examples thereof include carboxylic acids such as stearic acid, oleic acid, and versatic acid; aqueous solutions of inorganic acids, carbon dioxide gas, and the like.

  As a method for obtaining the modified conjugated diene polymer from the polymer solution, a known method can be used. For example, the solvent is separated from the polymer solution by, for example, steam stripping, the polymer is filtered, and the polymer is filtered and dehydrated and dried to obtain the polymer. The polymer solution is concentrated in a flushing tank. Furthermore, a method of obtaining a polymer by devolatilization with a vent extruder or the like, a method of obtaining a polymer by directly devolatilizing a polymer solution with a drum dryer or the like, and the like.

  The composition of this embodiment preferably contains 3% by mass to 99.9995% by mass of component (A), more preferably 5% by mass to 95% by mass, and 20% by mass to 80% by mass. More preferably, it is particularly preferably 30 to 70% by mass. If the component (A) is at least the lower limit in the composition, properties derived from the rubber material such as rubber elasticity and impact resistance can be added to the composition, and the component (A) is in the composition. If it is below the said upper limit, the other component which reinforces the weak points of rubber, such as heat resistance and a weather resistance, can be added to a composition.

<(B) component>
The component (B) used in the present embodiment is a compound represented by the following formula (1).
(In formula (1), _one of R _{1 to} R ₆ is an alkyl group having 1 to 6 carbon atoms, one is a hydrogen atom, two are thioether groups, and two are hydroxyl groups. is there.)

  The specific structure of (B) component will not be specifically limited if the conditions of Formula (1) are satisfy | filled. Although it does not specifically limit as said C1-C6 alkyl group, For example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group is mentioned. The thioether group is not particularly limited, and examples thereof include a butylthiomethyl group, a butylthioethyl group, a hexylthiomethyl group, a hexylthioethyl group, an octylthiomethyl group, and an octylthioethyl group. The two thioether groups may be the same or different.

The compositions of the present embodiment is different from the above component (A) 100 parts by weight, including the component (B) 5 × 10 ^-4 ~100 × 10 ^-4 parts by weight. If the content of the component (B) in the composition is 5 × 10 ⁻⁴ parts by mass or more with respect to 100 parts by mass of the component (A), the thermal stability of the composition is improved, If the content of the component (B) is 100 × 10 ⁻⁴ parts by mass or less with respect to 100 parts by mass of the component (A), the color tone of the composition will be good. In the composition of this embodiment, the content of the component (B) is preferably 10 × 10 ^{−4 to} 95 × 10 ⁻⁴ parts by mass with respect to 100 parts by mass of the component (A), and 20 × More preferably, it is 10 ^{−4 to} 90 × 10 ⁻⁴ parts by mass.

  The content of the component (B) in the composition can be analyzed by liquid chromatography. As a liquid chromatograph, for example, Acquity UPLC system (Waters) can be used, as a column, for example, HSS C18 (Waters) can be used, and as a detector, for example, charged A particle detector Corona Ultra RS (Nippon Dionex) can be used. The eluent is, for example, a mixed solution of (a) acetonitrile / (b) water, and the concentration of both starts from (a) 100%, changes to (a) 100% after 4 minutes, and holds for 6 minutes. 10 minutes after the start, (b) change to 100% and hold for 2 minutes. The eluent flow rate is 0.4 ml / min and the column temperature is 40 ° C.

In the compound represented by the above formula (1), the positional relationship between the alkyl group that is a substituent of the aromatic ring, the two thioether groups, and the two hydroxyl groups is not particularly limited, but the two hydroxyl groups are in the meta position. In the case where the two thioether groups are also in the meta position, it is preferable because the yellowing suppression effect of the composition is more exhibited. Specifically, the component (B) used in the present embodiment is preferably a compound represented by the following formula (1-1) and / or a compound represented by the following formula (1-2).

In formula (1-1), R ₁₆ is an alkyl group having 1 to 6 carbon atoms, and R ₁₇ and R ₁₈ are each independently an alkyl group having 4 to 12 carbon atoms.

In formula (1-2), R ₁₉ is an alkyl group having 1 to 6 carbon atoms, and R ₂₀ and R ₂₁ are each independently an alkyl group having 4 to 12 carbon atoms.

In the above formulas (1-1) and (1-2), specific examples of R ₁₆ and R ₁₉ are not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, when R ₁₆ and R ₁₉ are methyl groups, the composition is excellent in yellowing suppression effect, which is preferable.

R ₁₇ , R ₁₈ , R ₂₀ , and R ₂₁ are specifically alkyl groups having 4 to 12 carbon atoms. Among them, the octyl group is preferable because of its excellent yellowing suppression effect and dispersibility in the polymer. .

  When the component (B) is a compound represented by the formula (1-1) or the formula (1-2), the composition of the present embodiment includes the compound represented by the formula (1-1) and the formula (1). Only one of the compounds represented by -2) may be contained, or both of them may be contained.

The content of the component (B) with respect to 100 parts by mass of the component (A) is preferably 5 × 10 ^{−4 to} 100 × 10 ⁻⁴ parts by mass from the viewpoint of suppressing yellowing of the composition. From the viewpoint of the gel suppression effect, 10 × 10 ^{−4 to} 95 × 10 ⁻⁴ parts by mass are more preferable.

<(C) component>
In addition to the component (A) and the component (B), the composition of the present embodiment further contains (C) a compound represented by the following general formula (2) (hereinafter also referred to as “component (C)”). This is preferable because a more excellent yellowing suppression effect is exhibited.

In formula (2), among R _{7 to} R ₁₂ , one is an alkyl group having 1 to 6 carbon atoms, two are hydrogen atoms, two are thioether groups, and one is a hydroxyl group. .

  The specific structure of (C) component will not be specifically limited if the conditions of Formula (2) are satisfy | filled. Although it does not specifically limit as said C1-C6 alkyl group, For example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group is mentioned. The thioether group is not particularly limited, and examples thereof include a butylthiomethyl group, a butylthioethyl group, a hexylthiomethyl group, a hexylthioethyl group, an octylthiomethyl group, and an octylthioethyl group. The two thioether groups may be the same or different.

In the compound represented by the above formula (2), the positional relationship of the alkyl group, the two thioether groups, and the one hydroxyl group that are substituents of the aromatic ring is not particularly limited, but the two thioether groups are in the meta position. This is preferable because the yellowing suppression effect of the composition is more exhibited. Specifically, the component (C) used in the present embodiment is preferably a compound represented by the following formula (2-1).

In formula (2-1), R ₁₃ is an alkyl group having 1 to 6 carbon atoms, and R ₁₄ and R ₁₅ are each independently an alkyl group having 4 to 12 carbon atoms.

In the above formula (2-1), specific examples of R ₁₃ are not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. In the case where R ₁₃ is a methyl group, it is preferable because the yellowing suppression effect of the composition is excellent. R ₁₄ and R ₁₅ are specifically an alkyl group having 4 to 12 carbon atoms, and an octyl group is preferred because of its excellent yellowing suppression effect and excellent dispersibility in polymers.

  In the composition of this embodiment, the content of the component (C) is 0.01 to 1 part by mass with respect to 100 parts by mass of the component (A). When the content of the component (C) is 0.01 parts by mass or more with respect to 100 parts by mass of the component (A), the weather resistance of the composition is improved, and the content of the component (C) (A) If it is 1 mass part or less with respect to 100 mass parts of components, the mechanical characteristic of a composition will become favorable. In the composition of the present embodiment, the content of the component (C) is more preferably 0.05 to 1 part by mass, further preferably 0.1 to 100 parts by mass of the component (A). 0.9 parts by mass.

  The content of the component (C) in the composition can be analyzed by liquid chromatography (HPLC) in the same manner as the method for analyzing the content of the component (B).

  In the composition of this embodiment, it is preferable that (C) component is contained 0.01-1 mass part with respect to 100 mass parts of (A) component. In the composition of this embodiment, if (C) component is 0.01 mass part or more with respect to 100 mass parts of (A) component, it will be excellent in yellowing suppression, and if less than 1 weight part, A) Good dispersibility in the component.

<Other ingredients>
(Heat stabilizer)
Component (B) or component (C) may be used in combination with another heat stabilizer. These are not particularly limited as long as they are usually used in (co) polymers of conjugated dienes and / or aromatic vinyls. For example, they are composed of phenols, phosphoruss, sulfurs, amines and benzotriazoles. At least one heat stabilizer selected from the group is used. Of these, phenol stabilizers, phosphorus stabilizers, sulfur stabilizers and the like are particularly preferable.

  As the phenol-based stabilizer, conventionally known ones can be used, and are not particularly limited. For example, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methyl Japanese Patent Application Laid-Open No. 63-179953 and other patents such as phenyl acrylate, 2,4-di-t-amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate Acrylate compounds described in Kaihei 1-168643; 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl-3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidene- (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, 3, 9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5 , 5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5- Di-T-butyl-4-hydroxybenzyl) benzene, tetrakis (methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate) methane, triethyleneglycolbi (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate), alkyl-substituted phenolic compounds such as tocopherol; 6- (4-hydroxy-3,5-di-t-butylanilino) -2 , 4-bis-octylthio-1,3,5-triazine, 6- (4-hydroxy-3,5-dimethylanilino) -2,4-bis-octylthio-1,3,5-triazine, 6- ( 4-hydroxy-3-methyl-5-t-butylanilino) -2,4-bis-octylthio-1,3,5-triazine, 2-octylthio-4,6-bis- (3,5-di-t- And triazine compounds such as butyl-4-oxyanilino) -1,3,5-triazine; and the like.

  Although it does not specifically limit as a phosphorus stabilizer, For example, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (cyclohexylphenyl) phosphite, 2,2-methylenebis (4,6-di-t -Butylphenyl) octyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10 -Dihydro-9-oxa-10-phosphaphenanthrene-10-oxy Monophosphite stabilizers such as id, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene; 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl- Di-tridecyl phosphite), 4,4'-isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite), 4,4'-isopropylidene-bis (diphenyl monoalkyl (C12-C15)) Phosphite), 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-t-butylphenyl) butane, tetrakis (2,4-di-t-butylphenyl) -4, 4'-biphenylene diphosphite, cyclic neopentanetetraylbis (octadecyl phosphite), cyclic neopentane Lylebis (isodecyl phosphite), cyclic neopentanetetrayl bis (nonylphenyl phosphite), cyclic neopentanetetrayl bis (2,4-di-t-butylphenyl phosphite), cyclic neopentanetetrayl Examples thereof include diphosphite stabilizers such as bis (2,4-dimethylphenylphosphite) and cyclic neopentanetetraylbis (2,6-di-t-butylphenylphosphite).

  Although it does not specifically limit as a sulfur type stabilizer, For example, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate , Lauryl stearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10- And tetraoxaspiro [5,5] undecane.

  The amine stabilizer is not particularly limited, and examples thereof include 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 4- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) -1- (2- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl)- Examples include hindered amine stabilizers such as 2,2,6,6-tetramethylpiperidine.

  Although it does not specifically limit as a benzotriazole type stabilizer, For example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5 -Chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole Etc.

  These stabilizers can be used alone or in combination of two or more. The amount of the stabilizer used is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 1 part by mass per 100 parts by mass of the (A) conjugated diene polymer. These stabilizers can usually be added to the polymer solution as a hydrocarbon solvent solution after the aforementioned modification reaction step and before the solvent removal step.

(Additive)
The composition of this embodiment can add various additives to the (A) conjugated diene polymer after adding a lower organic terminator and a nonionic surfactant according to the objective. The other additives may be added simultaneously with or before the stabilizer. Specific examples of other additives include, but are not limited to, softeners such as oil; reinforcing agents such as silica and carbon black; dimethyl phthalate, diethyl phthalate, dihexyl phthalate, butyl lauryl phthalate, di (2-ethylhexyl) ) Phthalate, dilauryl phthalate, di-2-octyl phthalate, di-n-butyl adipate, diisooctyl adipate, octyl decyl adipate, di-2-ethylhexyl-4-thioazelate, diethyl sebacate, di-n-butyl malate, Plasticizers such as diethyl malate; titanium oxide, zinc white, lead white, red lead, cuprous oxide, iron black, cadmium yellow, molybdenum red, silver vermilion, yellow lead, chromium oxide, bitumen, barium sulfate, alumina white, white Inorganic pigments such as carbon, Coloring agents such as machine pigments; conductivity imparting agents such as ferrite; calcium carbonate, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, calcium silicate, magnesium silicate, calcium sulfate, Various additives such as inorganic fillers such as barium sulfate, calcium sulfite, mica, dolomite, clay, talc, zinc oxide and glass fiber; conductivity imparting agents such as ferrite; antistatic agent; nucleating agent; flame retardant; It is done. These additives can be used alone or in combination of two or more. Moreover, content of these additives is suitably determined in the range which does not impair the effect of this invention.

  The composition of this embodiment can be used by mixing with other resins depending on the application. Specific examples of the other resins are not particularly limited. For example, polymers of monomers such as ethylene, propylene, butene, butadiene, cyclohexene, isoprene, styrene, α-methylstyrene, acrylonitrile, acrylic acid, methacrylic acid, and acrylamide. And a copolymer.

  The composition of this embodiment can improve compatibility with polystyrene by polymerizing styrene after dissolving in a solvent containing a styrene monomer. Moreover, after dissolving the composition of this embodiment in the solvent containing styrene and acrylonitrile, the polymer excellent in impact resistance, heat resistance, and workability can be given by polymerizing styrene and acrylonitrile.

<Method for producing composition>
The method for producing the composition of the present embodiment is not particularly limited as long as it is a method capable of mixing the component (A) and the component (B) and, if necessary, other components such as the component (C). The mixing method may be any method in which each raw material component is mixed in a solution state or in a solvent-free state, but the component (B) or the component (C) is directly added to the component (A) in the solution state after polymerization. Alternatively, a method of diluting and mixing in a solvent is preferably used because each component has high uniform dispersibility.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

[Analysis method]
(1) Mooney viscosity Using a Mooney viscometer ("VR1132" manufactured by Kamijima Seisakusho Co., Ltd.), the Mooney viscosity of the compositions obtained in Examples and Comparative Examples was determined in accordance with the 2001 edition of JIS K6300 (ISO 289-1). It was measured. The measurement temperature was 100 ° C. First, after preheating the sample for 1 minute, the rotor was rotated at 2 rpm, and the torque after 4 minutes was measured to obtain the Mooney viscosity (ML _{1 + 4} ).

(2) Evaluation of heating yellowing (b value)
A test piece having a length of 4 cm, a width of 4 cm, and a thickness of 2 cm was prepared by press molding the compositions obtained in Examples and Comparative Examples. The prepared test piece was placed in an oven, and heating was continued at 80 ° C. for 1 hour in the presence of air. About the test piece after a heating, b value of the thickness direction was measured with the color difference meter. NDJ-400 manufactured by Nippon Denshoku Industries Co., Ltd. was used as a measuring instrument. The measurement method was reflection measurement.

[Stabilizer]
<(B) component>
(B-1) 2,4-dihydroxy-3,5-bis (octylthiomethyl) toluene (B-2) 2,6-dihydroxy-3,5-bis (octylthiomethyl) toluene <(C) Ingredient>
(C-1) 2,4-bis (octylthiomethyl) orthocresol (manufactured by Ciba Specialty Chemicals)

[Example 1]
An internal volume of 11 L, an internal height to diameter ratio (L / D) of 4, an autoclave (with a stirrer) having an inlet at the bottom, an outlet at the top, a stirrer and a temperature adjusting jacket A tank reactor) was used as the polymerization reactor.

  The temperature was set to 15 under the condition that impurities such as moisture were previously removed, under conditions of 1,3-butadiene 42.2 g / min, 1,2-butadiene 0.008 g / min, and n-hexane 198.8 g / min. The mixture was continuously fed to the bottom of the polymerization reactor while being adjusted to ° C. Furthermore, n-butyllithium as a polymerization initiator was supplied to the bottom of the polymerization reactor at a rate of 1.2 mmol / min to initiate the polymerization reaction. The internal temperature at the outlet of the polymerization reactor was adjusted to 100 ° C., and the polymerization reaction was continued to obtain a conjugated diene polymer solution.

Stabilizer (B-1), stabilizer (B-2), stabilizer (C-1) and water are added to the conjugated diene polymer solution flowing out from the top of the polymerization reactor, and 100 parts by mass of the conjugated diene polymer. In addition, 50 × 10 ⁻⁴ parts by mass, 50 × 10 ⁻⁴ parts by mass, 0.1 part by mass, and 10.0 parts by mass are added in succession, and carbon dioxide gas is further added. The resulting n-butyllithium was continuously added at a molar ratio (n-butyllithium: carbon dioxide) of 1: 1.5 to obtain a composition solution. The obtained composition solution was desolvated by steam stripping, and residual moisture was removed with an open roll to obtain a composition (1) composed of a stabilizer and polybutadiene.

  As a result of analysis, the obtained composition (1) had a Mooney viscosity at 100 ° C. of 42.5 and an appearance (b value) of 3.2.

[Examples 2 to 4 and Comparative Examples 1 to 4]
Except having changed the addition amount of various stabilizers as Table 1, it carried out similarly to Example 1, and obtained and analyzed the composition (2) -composition (8). The results are shown in Table 1.

Claims (2)

(A) 100 parts by mass of a conjugated diene polymer;
(B) 5 × 10 ^{−4 to} 100 × 10 ⁻⁴ parts by mass of a compound represented by the following formula (1),
A composition comprising :
(In formula (1), _one of R _{1 to} R ₆ is an alkyl group having 1 to 6 carbon atoms, one is a hydrogen atom, two are thioether groups, and two are hydroxyl groups. is there.)
The component (B) is a compound represented by the following formula (1-1) and / or represented by the following formula (1-2).
A composition which is a compound to be prepared.
(In the formula (1-1), R ₁₆ is an alkyl group having 1 to 6 carbon atoms, and R ₁₇ and R ₁₈ are
It is an alkyl group having 4 to 12 carbon atoms. )
(In the formula (1-2), R ₁₉ is an alkyl group having 1 to 6 carbon atoms, and R ₂₀ and R ₂₁ are
It is an alkyl group having 4 to 12 carbon atoms. ) (C) Compound 0 represented by the following formula (2) with respect to 100 parts by mass of component (A)
. The composition of claim 1 comprising 01 to 1 part by weight ,
(In formula (2), one of R _{7 to} R ₁₂ is an alkyl group having 1 to 6 carbon atoms, two are hydrogen atoms, two are thioether groups, and one is a hydroxyl group. is there.)
The composition according to claim 1, wherein the component (C) is a compound represented by the following formula (2-1).
.
(In the formula (2-1), R ₁₃ is an alkyl group having 1 to 6 carbon atoms, and R ₁₄ and R ₁₅ are
It is an alkyl group having 4 to 12 carbon atoms. )