TW201341459A - Resin composition, hydrogenated conjugate diene block copolymer and method for manufacturing the same and formed article - Google Patents

Abstract

A resin composition including a hydrogenated conjugate diene block copolymer and a method for manufacturing hydrogenated conjugate diene block copolymer are provided. The method has an excellent temporal stability and an excellent processability when compounding with a thermoplastic resin, etc., and can form a polymer alloy with excellent physical properties after compounding. A resin composition includes a hydrogenated conjugate diene block copolymer and at least one selected from a nonpolar polymer, a polar polymer and a filing agent. The hydrogenated conjugate diene block copolymer includes a group represented by formula (i), etc., and a silyl protection rate of N atom in a polar group including N atom is not less than 70%. [In formula (i), R1, R2 and R3 represent alkyl groups, etc.] The silyl protection rate (%)=(number of Si atom bonded on N atom of the polar group including N atom)/[(number of Si atom bonded on N atom of the polar group including N atom)+(number of H atom bonded on N atom of the polar group including N atom)]*100 (In above formula representing the silyl protection rate(%), the polar group including N atom is a generic term of a group represented by the formula (i) and a group obtained by removing at least one group represented by -SiR1R2R3 in the group represented by the formula (i)).

Description

Resin composition and method for producing hydrogenated conjugated diene block copolymer

The present invention relates to a resin composition containing a hydrogenated conjugated diene block copolymer, a method for producing a hydrogenated conjugated diene block copolymer, and a copolymer obtained by the above production method, comprising the above A resin composition of a copolymer and a molded body comprising the above resin composition.

a hydrogenated product of a block copolymer formed of a conjugated diene compound and an aromatic alkenyl compound, that is, a hydrogenated block copolymer, and a nonpolar resin such as a polyolefin resin or a polystyrene resin, and an ethylene-propylene rubber Since the compatibility of non-polar rubbers is relatively high, various compositions containing hydrogenated block copolymers are widely used as compatibilizers.

However, hydrogenated block copolymers and polyethylene terephthalate (PET) or acrylonitrile/butadiene/styrene copolymers (ABS), nylon and other polarities Since the compatibility of the resin is low, in order to ensure physical properties to be used, it is necessary to impart a polar group to the hydrogenated block copolymer. For example, in Patent Document 1 to Patent Document 3, An amine-modified hydrogenated conjugated diene block copolymer and a polymer alloy copolymerized with the hydrogenated conjugated diene block are shown.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-298797

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-320399

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-272695

The existing amine-modified hydrogenated conjugated diene block copolymer has a problem of lacking stability over time due to the presence of a reactive amine group in the copolymer, and further, the above-mentioned copolymer is produced. When it is a compound with another thermoplastic resin or the like, there is a problem that the workability is poor and the physical properties of the polymer alloy after the composite are inferior. In particular, when the above-mentioned copolymer is placed in a hot and humid environment and then alloyed, the physical properties of the obtained polymer alloy are not satisfactory.

An object of the present invention is to provide a resin composition containing a hydrogenated conjugated diene block copolymer, which is excellent in stability over time and workability in combination with a thermoplastic resin or the like, and is excellent in physical properties after compounding. A method for producing a hydrogenated conjugated diene block copolymer of an alloy, and a polymer alloy obtained thereby.

The inventors of the present invention have conducted intensive studies in order to solve the above problems. As a result, it has been found that the above problems can be solved by the production method having the following constitution, and the present invention has been completed. That is, the present invention is, for example, the following [1] to [9].

[1] A resin composition comprising a hydrogenated conjugated diene block copolymer and at least one selected from the group consisting of a nonpolar polymer, a polar polymer, and a filler, the hydrogenated conjugated diene block copolymer Containing at least one group selected from the group represented by the formula (i), the group represented by the formula (ii), and the group represented by the formula (iii), and the polarity of the N atom-containing group determined as follows The sulfonyl group protection ratio of the N atom of the group is 70% or more;

In the formulae (i) to (iii), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Or an organic decyloxy group having 1 to 100 carbon atoms; R ⁴ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms; and R ⁵ represents a carbon number of 1 ~12 divalent hydrocarbon group]; decyl group protection ratio (%) = (Si atom bonded to N atom in a polar group containing N atom) / [(bonded to a polar group containing a N atom) Si atom(s) on the N atom in the middle) + (hydrogen atom bonded to the N atom in the polar group containing the N atom)] × 100

(In the formula indicating the decyl group protection ratio (%), the polar group containing the N atom means a group represented by the formula (i) to the formula (iii), and the formula (i) (iii) at least one of the groups represented by -SiR ¹ R ² R ³ or -SiR ¹ R ² -R ⁵ -SiR ¹ R ² - a group derived from the group represented by the group).

[2] A method for producing a hydrogenated conjugated diene block copolymer, comprising the steps of: (1) having a group selected from the group represented by formula (i), a group represented by formula (ii), and a step of hydrogenating a conjugated diene block copolymer of at least one of the groups represented by formula (iii); (2) a hydrogenated conjugated diene block obtained from the above step (1) In the reaction solution of the copolymer and the solvent, the solvent is removed by at least one selected from the following (a) to (c): (a) by contacting the reaction solution and the aqueous alkaline solution with steam. a method of removing a solvent, (b) a method of continuously or intermittently supplying the reaction liquid to a vessel maintained at 50 ° C to 260 ° C and 0.01 kPa to 0.1 MPa, and (c) supplying the reaction liquid a method of rotating a rotating drum roll heated to 80 ° C to 260 ° C;

In the formulae (i) to (iii), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Or an organic decyloxy group having 1 to 100 carbon atoms; R ⁴ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms; and R ⁵ represents a carbon number of 1 ~12 divalent hydrocarbon group].

[3] The production method according to [2] above, wherein the step of removing the solvent described above (2) In the case of the method (a), the temperature of the alkaline aqueous solution is from 50 ° C to 150 ° C.

[4] The production method according to [2] or [3] above, wherein, in the case where the step (2) of removing the solvent is the method (a), the pH of the alkaline aqueous solution is 8 or more.

[5] The production method according to any one of [2] to [4] wherein the conjugated diene block copolymer is a polymer block selected from the group consisting of (A) to (D) below. Block copolymers of two or more polymer blocks: (A) an aromatic alkenyl polymer block having an aromatic alkenyl compound unit amount of 80% by mass or more; (B) a conjugated diene compound unit amount of 80% by mass or more, and a 1,2 bond content and 3, The conjugated diene polymer block having a total content of 4 bonds is less than 30 mol%; (C) the conjugated diene compound unit amount is 80% by mass or more, and the 1, 2 bond content and the 3, 4 bond content are 30 mol in total. % to 90 mol% of a conjugated diene polymer block; (D) a conjugated diene compound unit amount of more than 20% by mass and less than 80% by mass of a conjugated diene compound and an aromatic alkenyl compound randomly A polymer copolymer block.

[6] The production method according to any one of the above [2] to [5] wherein the conjugated diene block copolymer is at least one selected from the group consisting of the following [A] to [E] The polymer obtained by a method: [A] at least reacting a conjugated diene compound in the presence of an organic alkali metal compound having at least one group represented by the above formula (i) to formula (iii) to obtain a conjugated second a method of an olefin block copolymer; [B] a method of reacting at least a conjugated diene compound with an unsaturated monomer having at least one group represented by the above formula (i) to formula (iii) to obtain a conjugated diene block copolymer; C] reacting a polymerization terminator having at least one group represented by the above formula (i) to formula (iii) with an active site of at least a block copolymer obtained by polymerizing a conjugated diene compound to obtain a conjugated second a method of an olefin block copolymer; [D] a coupling copolymer obtained by polymerizing a coupling agent having at least one group represented by the above formula (i) to formula (iii) with at least a conjugated diene compound a living point reaction to obtain a conjugated diene block copolymer; [E] an unsaturated monomer having at least one group represented by the above formula (i) to formula (iii) and at least conjugated A method of reacting an active spot of a block copolymer obtained by polymerization of a diene compound to obtain a conjugated diene block copolymer.

[7] A hydrogenated conjugated diene block copolymer obtained by the production method according to any one of [2] to [6] above.

[8] A resin composition containing the hydrogenated conjugated diene block copolymer of [7] above and at least one selected from the group consisting of a nonpolar polymer, a polar polymer, and a filler.

[9] A molded body obtained by molding the resin composition of the above [1] or [8].

According to the present invention, there can be provided a resin composition containing a hydrogenated conjugated diene block copolymer having a functional group having a high alkylidene group protection ratio. In addition, it is possible to provide a method for producing a hydrogenated conjugated diene block copolymer of a polymer alloy which is excellent in workability at the time of recombination with a thermoplastic resin or the like, and which is excellent in physical properties after recombination. The resulting polymer alloy. Further, even when the obtained copolymer is placed in a hot and humid environment and then alloyed, the physical properties of the obtained polymer alloy are also excellent.

In the present specification, the alkyl group has a carbon number of 1 to 20, preferably 1 to 18, more preferably 1 to 6 as long as it is not particularly mentioned, and the aryl group has 6 to 20 carbon atoms, preferably 6 to 6 carbon atoms. 12, more preferably 6 to 9, the aralkyl group has a carbon number of 7 to 20, preferably 7 to 13, more preferably 7 to 10, and the organodecyloxy group has a carbon number of 1 to 100, preferably 1 Preferably, the carbon number of the alkylene group or the alkylene group is from 1 to 20, more preferably from 1 to 10, more preferably from 1 to 6, and the carbon number of the trialkyldecyl group is more preferably from 5 to 30. Good for 3~18, better for 3~9, and then better for 3~6.

In the present invention, examples of the organodecyloxy group include the following structures. The upper limit of the carbon number of the organodecyloxy group is 100, preferably 50, more preferably 30.

[Chemical 3]

In the formula, r is not particularly limited as long as the upper limit of the carbon number of the organodecyloxy group satisfies the above requirements, and is usually 0 or a positive integer, and preferably an integer of 0 to 5. In the formula, R each independently represents an organic group. Examples of the organic group include an alkyl group, an aryl group, a polyether group, and a fluorine-containing group.

The alkyl group may be a straight chain, a branched chain or a cyclic group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a second butyl group, a tert-butyl group, a pentyl group, and a cyclopentyl group. The cyclohexyl group is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The aryl group is preferably a phenyl group. Examples of the polyether group include a polyoxyethylene group, a polyoxypropylene group, and a polyoxyethylene/polyoxypropyl group. Examples of the fluorine-containing group include an alkyl group and an alkenyl group having one or more fluorine atoms as a substituent. Here, the alkyl group and the alkenyl group may be a straight chain, a branched chain or a cyclic group.

Specific examples of the organic decyloxy group include 1,1,1,3,3-pentamethyldidecyloxy, 1,1,1,3,3-pentaethyldidecyloxy, 1,1. 1,3,3-pentaphenyldioxyloxy.

In the present specification, the group represented by the formula (i) to the formula (iii) is also referred to as "specific group"; -SiR ¹ R ² R ³ or -SiR ¹ R ² -R ⁵ -SiR in a specific group a group represented by ¹ R ² - is also referred to as a "protecting group"; a group derived from a specific group and at least one protecting group in a specific group (for example, represented by formula (i) and formula (iii)) In the case of a group, -NH ₂ , and in the case of the group represented by the formula (ii), -NHR ⁴ ) is also collectively referred to as "a polar group containing a N atom". In addition, a polymer having a polar group containing an N atom is also referred to as a "modified polymer", and an active point of the polymer is also referred to as a "polymerization end", and hydrogenation is also referred to as "hydrogenate". The hydrogenated polymer is also referred to as "hydrogenated polymer", and the structural unit derived from the compound X in the polymer is also referred to as "compound X unit".

[Method for Producing Hydrogenated Conjugated Diene Block Copolymer]

The method for producing a hydrogenated conjugated diene block copolymer of the present invention comprises the steps of: (1) copolymerizing a conjugated diene block having at least one group represented by formula (i) to formula (iii); a step of hydrogenating the material; (2) a reaction liquid containing the hydrogenated conjugated diene block copolymer obtained in the step (1), by at least one selected from the group consisting of (a) to (c) described later The step to remove the solvent.

In the present specification, the conjugated diene block copolymer having at least one group represented by formula (i) to formula (iii) which is hydrogenated in the step (1) is also referred to as "conjugated diene block". The copolymer A", the hydrogenated conjugated diene block copolymer obtained in the step (1) is also referred to as "hydrogenated conjugated diene block copolymer B", and the polymerization obtained in the step (2) Also known as "hydrogenated conjugated diene block copolymer C".

[Chemical 4]

In the formulae (i) to (iii), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Or an organodecyloxy group having 1 to 100 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, and preferably -SiR ¹ R ² R ³ in the formula (i) and the formula (ii) is a carbon number of 3 ~18 trialkylsulfonyl. R ⁴ represents alkyl having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, preferably represents an alkyl group having 1 to 20. R ⁵ represents a divalent hydrocarbon group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 12 carbon atoms, and particularly preferably an ethyl group.

Hereinafter, the features of the present invention will be described.

The recovery of the polymer contained in the polymer solution produced by solution polymerization is usually carried out by washing the polymer solution, removing the catalyst residue, etc., and then performing devolatilization treatment from the polymer. Solvent and unreacted monomers are removed from the solution (hereinafter also referred to as "desolvation").

According to the prior art manufacturing method, the solvent removal is usually carried out by contacting neutral steam with a polymer solution. Therefore, the hydrogenated conjugated diene block copolymer having a specific group (the group obtained by protecting the N atom by a protecting group such as -SiR ¹ R ² R ³ ) is deprotected by the above-described solvent removal step. Therefore, in the finally obtained polymer, the protection ratio of the protecting group to the N atom becomes low. In addition, it is generally believed that such protection is preferably removed in this manner.

However, as a result, the properties of the hydrogenated conjugated diene block copolymer obtained over time, the workability at the time of recombination with a thermoplastic resin or the like, and the physical properties of the polymer alloy after the composite are insufficient. In particular, when the obtained copolymer is placed in a hot and humid environment and mixed with a thermoplastic resin or the like to form a polymer alloy, the physical properties of the obtained polymer alloy are not satisfactory.

With respect to the above conventional production method, according to the production method of the present invention, since the reaction liquid containing the hydrogenated conjugated diene block copolymer B is subjected to a specific solvent removal step, it is considered that the protection ratio of the alkyl group is maintained. The protection of the N atom by the predetermined protecting group results in the stability of the hydrogenated conjugated diene block copolymer C finally obtained (for example, the Melt Flow Rate is standard), and a thermoplastic resin or the like. The workability at the time of compounding and the physical properties of the polymer alloy are excellent. For example, by using a resin composition containing a hydrogenated conjugated diene block copolymer C, heat resistance, rigidity, impact resistance, surface impact resistance, tensile elongation at break, specularity, and interlayer can be produced. A molded body excellent in balance such as peelability.

Hereinafter, the hydrogenated conjugated diene block copolymer C obtained by the production method of the present invention will be described. In addition, the details of the conjugated diene block copolymer A used in the present invention will be described later.

In the hydrogenated conjugated diene block copolymer C, the content of the polar group having a N atom is preferably 0.1 in terms of the processability at the time of compounding with a thermoplastic resin or the like with respect to one molecular chain of the polymer. ~5, especially good 0.4 to 3. The content of the polar group containing a N atom is also referred to as "modified mass". Polar group containing N atom The details of the measurement conditions of the content (modified mass) are as described in the examples.

In the N-containing polar group of the hydrogenated conjugated diene block copolymer C, the N-alkyl has a decyl group-protection ratio of 70% or more, preferably 80% or more, and particularly preferably 90% or more. The upper limit of the decyl group protection ratio of the N atom is not particularly limited, and is, for example, 100%, and there is no practical problem even if the upper limit is about 99%.

Further, the polar group containing a N atom may be simply referred to as a "polar group".

The decyl group protection ratio of the N atom is represented by the following formula.

矽 alkyl protection ratio (%) = Si atom bonded to N atom in a polar group containing N atom / (Si atom bonded to N atom in a polar group containing N atom) + a hydrogen atom bonded to an N atom in a polar group containing a N atom (a) × 100

In the case where the protecting group is an alkyl decyl group, the decyl group protecting ratio is represented by the following formula.

矽alkyl protection ratio (%) = alkyl decyl group bonded to N atom in a polar group containing a N atom / alkyl decane bonded to N atom in a polar group containing a N atom a hydrogen atom on a N atom bonded to a polar group containing a N atom (a) × 100

The alkylene group protection ratio can be obtained by purifying the hydrogenated conjugated diene block copolymer C, using deuterated chloroform as a solvent, and according to ¹ H-nuclear magnetic resonance (NMR) spectrum at 400 MHz. To calculate.

The melt flow rate (MFR: 230 ° C, 2.16 kg) measured by Japanese Industrial Standards (JIS) K7210 of the hydrogenated conjugated diene block copolymer C is usually 0.1 g/10 min or more, preferably 0.1 g/10 min or more. It is from 0.5 g/10 min to 100 g/10 min, more preferably from 0.5 g/10 min to 50 g/10 min. In addition, the details of the measurement conditions of MFR are as described in the examples. Since the above-mentioned copolymer has a high protection ratio of N atoms in a polar group containing an N atom, it is excellent in stability over time, and for example, the retention of MFR is high even after heating promotion.

Hereinafter, each step of the production method of the present invention will be described.

<step 1)>

In the step (1), the conjugated diene block copolymer A having a specific group is hydrogenated. The method of hydrogenation and the reaction conditions are not particularly limited, and for example, it is carried out under the pressure of hydrogen gas at 20 ° C to 150 ° C and 0.1 MPa to 10 MPa in the presence of a hydrogenation catalyst.

The hydrogenation ratio of the hydrogenated conjugated diene block copolymer B obtained in the step (1) can be arbitrarily selected by changing the amount of the hydrogenation catalyst, the hydrogen pressure at the time of the hydrogenation reaction, the reaction time, and the like. In terms of improvement in weather resistance, the hydrogenation rate is usually 10% or more, preferably 50% or more, more preferably 80% or more, and particularly preferably 95% or more of the aliphatic double bond derived from the conjugated diene compound. . In addition, the details of the measurement conditions of the hydrogenation rate are described in the examples.

As the hydrogenation catalyst, a compound containing any one of Group 4, Group 5, Group 6, Group 7, Group 8, Group 9, Group 10 elements of the periodic table, for example, contains Ti, V, Co, Ni, Zr, Ru. a compound of Rh, Pd, Hf, Re, Pt.

Specific examples of the hydrogenation catalyst include metallocene compounds containing Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, Re, etc., and Pd, Ni, Pt, Rh, and Ru. A supported heterogeneous catalyst supported on a carrier such as carbon, silica, alumina or diatomaceous earth, an organic salt of Ni, Co or the like, and an aluminum acetonide salt and an organoaluminum A homogeneous ziegler type catalyst such as a combination of reducing agents, an organometallic compound or a complex of Ru, Rh, etc., and a fullerene or carbon nanotube (hydrogen) which absorbs hydrogen. Nanotube).

Among these, a metallocene compound containing any one of Ti, Zr, Hf, Co, and Ni is preferable from the viewpoint of performing a hydrogenation reaction in a homogeneous phase in an inert organic solvent. Further, a metallocene compound containing any one of Ti, Zr, and Hf is preferred. In particular, a hydrogenation catalyst obtained by reacting a titanocene compound with an alkyllithium is preferred as a catalyst which is inexpensive and industrially particularly useful.

Specific examples include, for example, Japanese Patent Laid-Open No. Hei 1-275605, Japanese Patent Laid-Open No. Hei 5-271326, Japanese Patent Laid-Open No. Hei 5-271325, Japanese Patent Laid-Open No. Hei 5-222115, and Japanese Patent No. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The hydrogenation catalyst described in Japanese Patent Publication No. Hei 7-90017, Japanese Patent Publication No. Sho 43-19960, and Japanese Patent Publication No. Sho 47-40473.

The hydrogenation catalyst may be used alone or in combination of two or more.

<Step (2)>

In the step (2), the reaction liquid containing the hydrogenated conjugated diene block copolymer B and the solvent obtained in the step (1) (hydrogenation step) is selected from the following (a) to (c) At least one of the methods removes the solvent. Among these, the method of (a) is preferable because it is excellent in industrial handleability.

(a) A method of removing a solvent by bringing the reaction liquid and the alkaline aqueous solution obtained in the step (1) into contact with steam such as steam (hereinafter also referred to as "steam stripping process (a)") .

(b) a method in which the reaction liquid obtained in the step (1) is continuously or intermittently supplied to a vessel maintained at 50 ° C to 260 ° C and 0.01 kPa to 0.1 MPa (hereinafter also referred to as "flash evaporation method" (flash evaporation process) (b)").

(c) A method of supplying the reaction liquid obtained in the step (1) to a rotating drum roll heated to 80 ° C to 260 ° C (hereinafter also referred to as "drum drying process (c)").

The concentration of the hydrogenated conjugated diene block copolymer B to be supplied to the reaction liquid obtained in the step (1) of the step (2) is preferably from 1% by mass to 70% by mass, more preferably 3% by mass. 60% by mass. If the concentration is within the above range, there is no operational obstacle.

The solvent to be used in the production of the conjugated diene block copolymer A is exemplified, and examples thereof include an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, and an aromatic hydrocarbon solvent.

Steam Stripping Method (a)

The steam stripping method is, for example, by reacting the reaction liquid obtained in the step (1) and A method in which a mixed solution of an alkaline aqueous solution is contacted with steam to remove a solvent. The steam stripping method has advantages such as excellent industrial workability.

The mixing ratio of the reaction liquid and the alkaline aqueous solution obtained in the step (1) is usually 10 parts by mass to 10,000 parts by mass, preferably 20 parts by mass to 2000 parts by mass, per 100 parts by mass of the reaction liquid. More preferably, it is 25 mass parts - 500 mass parts. The temperature in the system is usually from 80 ° C to 200 ° C, preferably from 90 ° C to 130 ° C. In addition, "inside the system" means the liquid phase in the reaction container, that is, the above mixed liquid.

The alkaline aqueous solution mixed with the above reaction liquid preferably satisfies the following conditions: that is, the pH of the alkaline aqueous solution at 80 ° C is preferably 8 or more, more preferably 8 to 12, and particularly preferably 8 to 11. When an alkaline aqueous solution having a pH in the above range is used, a polymer having excellent stability over time such as a high alkyl group protection ratio and a melt flow rate (Melt Flow Rate) can be obtained. Further, the pH is measured by a glass electrode method. The temperature of the alkaline aqueous solution mixed with the above reaction liquid is preferably from 50 ° C to 150 ° C, more preferably from 60 ° C to 140 ° C, particularly preferably from 70 ° C to 130 ° C.

The alkaline aqueous solution is an aqueous solution obtained by adding an alkali compound to adjust the pH to a basicity, and examples of the alkali compound include sodium nitrite, ammonia, ammonium hydroxide, ammonium hydrogencarbonate, sodium hydroxide, sodium citrate, and sodium hydrogencarbonate. , disodium carbonate, potassium hydroxide, calcium hydroxide, barium hydroxide, copper hydroxide, aluminum hydroxide, iron hydroxide, sodium aluminate, sodium sulfide, sodium thiosulfate, sodium nitrite, potassium carbonate Calcium nitrite, magnesium hydroxide, sodium sulfite, potassium carbonate, calcium nitrite, magnesium hydroxide, sodium pyrophosphate, sodium tripolyphosphate, potassium pyrophosphate, lithium hydroxide. Among these, ammonia, sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferred.

The base compounds may be used alone or in combination of two or more.

The contact treatment by steam may, for example, be a method in which an aqueous solution adjusted to be alkaline is added to a desolvation tank, steam is blown thereinto, adjusted to a predetermined temperature, and the reaction liquid is introduced; and the reaction is carried out in a solvent removal tank. a method in which a liquid is mixed with an aqueous alkaline solution, and then the resulting mixed solution is brought into contact with steam; and a method in which the aqueous solution in the desolvation tank is brought into contact with steam while the reaction liquid is added to the solvent removal tank, and the embodiment thereof There is no particular limitation.

The steam temperature is usually from 110 ° C to 420 ° C, preferably from 110 ° C to 200 ° C. The steam stripping treatment time is usually from 10 minutes to 8 hours, preferably from 30 minutes to 6 hours. When the contact treatment is carried out under such conditions, a polymer having a high stability ratio such as a high alkyl group and a melt flow rate and the like can be obtained, and this is preferable.

In the steam stripping method, it is preferred to provide a drying step after contacting the mixed liquid with steam. The drying temperature here is usually from 80 ° C to 260 ° C, preferably from 100 ° C to 220 ° C. For example, a heat roller can be used in the drying step.

"Jet Evaporation Method (b)"

The rapid evaporation method is to continuously or intermittently supply the reaction liquid obtained in the step (1) to a temperature of 50 ° C to 260 ° C and 0.01 kPa to 0.1 MPa, preferably 60 ° C to 180 ° C and 0.01 kPa. A method of vaporizing and removing a solvent in a container under conditions of 0.05 MPa. The flash evaporation method has the advantages of running cost, low cost of the device, and simple steps.

The reaction liquid is preferably heated at the above temperature before being introduced into a flash evaporation drum used in the flash evaporation method, and the heating method thereof may be listed, for example. A method of heating by a heat exchanger. Alternatively, the reaction solution may be appropriately concentrated before being introduced into a flash evaporation drum.

"Drum drying method (c)"

The drum drying method is a method in which the reaction liquid obtained in the step (1) is supplied to a rotating drum roll heated to 80 ° C to 260 ° C, preferably 100 ° C to 220 ° C, to vaporize and remove the solvent. The solvent removal here can be carried out under normal pressure conditions or under reduced pressure. In addition, the time required is about 3 minutes to 30 minutes. Moreover, it is preferable that the reaction liquid obtained in the step (1) is directly supplied to the rotating drum roll without being brought into contact with another aqueous solution or the like.

For example, the reaction liquid obtained in the step (1) is continuously supplied to a drum heated to the above temperature by introducing a heat medium (for example, water vapor) inside the rotating drum, evaporating and concentrating, and simultaneously making the reaction liquid The film adhered to the surface of the drum, and the blade was continuously peeled off from the surface of the drum during a period in which the drum was rotated by a fixed blade.

The drum drying method has the advantages that a homogeneous target can be obtained, and both the desolvation and drying operations can be handled by one apparatus, and the solvent can be removed and dried by a heat transfer heating method, so that the heat efficiency is excellent.

The type of the drum drying is not particularly limited, and examples thereof include a double drum type, a twin drum type, and a single drum type. Further, the single-drum type liquid supply method may, for example, be a dip feed type, a spray feed type, a splash feed type, an upper roll liquid supply type, or a side roll liquid supply type. (side roll feed) type, lower roll transfer type.

By carrying out the above various steps, the desolvated hydrogenated conjugated diene block copolymer C can be obtained. The residual amount of the solvent in the hydrogenated conjugated diene block copolymer C is usually 3% by mass or less, preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. The copolymer C obtained by the production method of the present invention has a characteristic that the N atom has a high sulfonyl group protection ratio and is excellent in various physical properties described above.

[Conjugated diene block copolymer A]

The conjugated diene block copolymer A to be supplied to the step (1) used in the present invention has a group selected from the above formula (i), a group represented by the formula (ii), and a formula (iii). At least one of the groups represented by the group (specific group).

The molecular weight of the conjugated diene block copolymer A is usually from 30,000 to 2,000,000, preferably from 30,000 to 2,000,000, based on the weight average molecular weight of the polystyrene conversion by the gel permeation chromatography (GPC) method. 40,000 to 1 million, more preferably 50,000 to 500,000. In addition, the details of the measurement conditions of the weight average molecular weight are as described in the examples.

The conjugated diene block copolymer A can be produced, for example, according to the method described in Japanese Patent No. 3134504, Japanese Patent No. 3360411, and Japanese Patent No. 3984495.

The method for producing the conjugated diene block copolymer A can be, for example, [A] reacting a conjugated diene compound or a conjugated diene compound with another monomer in the presence of an organic alkali metal compound having a specific group. a method of obtaining a conjugated diene block copolymer A; [B] a conjugated diene compound and an unsaturated monomer having a specific group, as needed a method in which a monomer other than the above unsaturated monomer is reacted together to obtain a conjugated diene block copolymer A; [C] a polymerization stopper having a specific group and a conjugated diene compound or conjugated a method in which a diene compound is reacted with an active point of a block copolymer obtained by polymerization of another monomer to obtain a conjugated diene block copolymer A; [D] a coupling agent having a specific group and a conjugated diene a method in which a compound or a conjugated diene compound is reacted with an active point of a block copolymer obtained by polymerization of another monomer to obtain a conjugated diene block copolymer A; [E] an unsaturated single having a specific group The method of reacting an active point of a block copolymer obtained by polymerizing a conjugated diene compound or a conjugated diene compound with another monomer to obtain a conjugated diene block copolymer A.

The conjugated diene block copolymer A is usually obtained by anionic polymerization of a conjugated diene compound and, if necessary, other monomers in a solvent. Examples of the solvent include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; alicyclic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; and benzene; An aromatic hydrocarbon solvent such as xylene, toluene or ethylbenzene. The solvent may be used alone or in combination of two or more.

The polymerization temperature is usually -10 ° C to 150 ° C, preferably 0 ° C to 120 ° C. The polymerization pressure is not particularly limited as long as it is carried out within a sufficient pressure to maintain the monomer and the solvent in the liquid phase at the polymerization temperature. The environment in the polymerization system is preferably replaced with an inert gas such as nitrogen.

In order to produce a conjugated diene block copolymer A having a specific group, it can be single The various methods of [A] to [E] described above can be carried out separately or in combination. The combination of various methods may be exemplified by a method of polymerizing a conjugated diene compound and an unsaturated monomer having a specific group in the presence of an organic alkali metal compound having a specific group ([A] and [B]); A method in which polymerization is carried out in the presence of an organic alkali metal compound having a specific group, followed by reacting a polymerization stopper having a specific group with an active site of the obtained polymer ([A] and [C]); Polymerization in the presence of an organic alkali metal compound, followed by a method of reacting a coupling agent having a specific group with an active site of the obtained polymer ([A] and [D]); and an organic alkali metal compound having a specific group A method in which polymerization is carried out in the presence of an unsaturated monomer having a specific group and an active point of the obtained polymer ([A] and [E]).

The components which can be preferably used in the above production method are exemplified below.

Polymerization Initiator

In the above polymerization reaction, a polymerization initiator can be used. The polymerization initiator may, for example, be an organic alkali metal compound having a specific group or an organic alkali metal compound having no specific group. In the case of using an organic alkali metal compound having a specific group, it corresponds to the method of the above [A].

The amount of the organic alkali metal compound to be used is usually 0.02 parts by mass to 15 parts by mass, preferably 0.03 parts by mass to 5 parts by mass, based on 100 parts by mass of the total of the conjugated diene compound and other monomers.

The polymerization initiators may be used alone or in combination of two or more.

Organic alkali metal compound having a specific group

The organic alkali metal compound having a specific group can be exemplified by the formula (1). An organic alkali metal compound represented. When the above compound is used, practical anionic polymerization can be carried out industrially efficiently.

[Chemical 5] XR ⁶ -Li (1)

Formula (1), X represents any one of formulas (I) - Formula (iii) a group represented by a, R ⁶ represents an alkylene group having a carbon number of 1 to 20 carbon atoms or an alkylene group having 1 to 20, more Jia is an alkylene group having a carbon number of 1 to 20.

The organic alkali metal compound represented by the formula (1) is exemplified by 3-litho-1-[N,N-bis(trimethyldecyl)aminopropane (3-lithio-1-[N,N). -bis(trimethylsilyl)]aminopropane), 2-lithium-1-[N,N-bis(trimethyldecyl)aminoethane, 3-litho-2,2-dimethyl-1- [N,N-bis(trimethyldecyl)]aminopropane, 3-lithium-1-[N-(t-butyl-dimethylalkylalkyl)-N-trimethyldecyl]amine Propane, 3-litho-1-[N-{bis(tert-butyl)-methyldecyl}-N-trimethyldecyl]aminopropane, 3-lithium-1-[N- (t-butyl-dimethylalkylalkyl)-N-trimethyldecylalkyl]aminoethane, 3-lithium-1-[N-{di(t-butyl)-methyldecyl] -N-trimethyldecyl]aminoethane, 3-litho-2,2-dimethyl-1-[N-(t-butyl-dimethylalkyl)-N-trimethyl Alkylalkyl]aminopropane, 3-litho-2,2-dimethyl-1-[N-{bis(tert-butyl)-methyldecyl}}-N-trimethyldecyl]amino An organic alkali metal compound having a group represented by the formula (i) such as propane; 3-litho-1-(N-methyl-N-trimethyldecyl)aminopropane, 3-lithium-1- (N- Ethyl-N-trimethyldecylalkyl)aminopropane, 2-lithium-1-(N-methyl-N-trimethyldecyl)aminoethane, 2-lithium-1-(N) -ethyl-N-trimethyldecylalkyl)aminoethane, 3-lithium-1-[N-methyl-N-(t-butyl-dimethyldecyl)aminopropane, 3 -litho-1-[N-methyl-N-{bis(t-butyl)-methyldecyl}}aminopropane, 3-litho-1-[N-ethyl-N-( Tributyl-dimethylalkylalkyl)]aminopropane, 3-litho-1-[N-ethyl-N-{bis(tert-butyl)-methyldecyl]}aminopropane, 3 -litho-1-[N-methyl-N-(t-butyl-dimethylmethylalkyl)]aminoethane, 3-lithium-1-[N-methyl-N-{di( Tert-butyl)-methyldecyl}}aminoethane, 3-lithium-1-[N-ethyl-N-(t-butyl-dimethylmethyl)alkyl)ethane, Organic alkali metal compound having a group represented by formula (ii), such as 3-litho-1-[N-ethyl-N-{bis(t-butyl)-methyldecyl]}aminoethane ; 2,2,5,5-tetramethyl-1-(3-lithopropyl)-1-aza-2,5-diindole cyclopentane (2,2,5,5-tetramethyl- 1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane), 2,2,5,5-tetramethyl-1-(3-litho-2,2-dimethyl-propyl) -1-nitrogen -2,5-dihalogenated cyclopentane, 2,2,5,5-tetramethyl-1-(2-lithoethyl)-1-aza-2,5-diindole cyclopentane An organic alkali metal compound having a group represented by the formula (iii).

Among these, 3-litho-1-[N,N-bis(trimethyldecyl)aminopropane, 2-lithium-1-[N,N-bis(trimethyldecane) is preferred. A) ethane, 3-litho-2,2-dimethyl-1-[N,N-bis(trimethyldecyl)aminopropane.

Organic alkali metal compound without specific group

Examples of the organic alkali metal compound having no specific group include an organolithium compound and an organic sodium compound, and among these, an organolithium compound is preferred. Organic lithiation Examples of the compound include an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound.

Examples of the organolithium compound include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, second butyl lithium, t-butyl lithium, pentyl lithium, hexyl lithium, cyclohexyl lithium, and benzene. Lithium, hexamethylene dilithium, cyclopentadienyllithium, indenyl lithium, 1,1-diphenyl-n-hexyllithium, 1,1-diphenyl-3-methylpentyl Lithium, lithium naphthalene, butadienyl dilithium, isopropenyl dilithium, m-diprenyl dilithium, 1,3-phenylene-bis-(3-methyl-1-phenyl 1,3-phenylene-bis-(3-methyl-1-phenylpentylidene)bislithium, 1,3-phenylene-bis-(3-methyl-1,[4-methylbenzene (i-pentylene) dilithium, 1,3-phenylene-bis-(3-methyl-1,[4-dodecylphenyl]pentylene) dilithium, 1,1,4, 4-tetraphenyl-1,4-dilithium butane, polybutadienyllithium, polyisoprenyllithium, polystyrene-butadienyllithium, polystyryllithium, polyvinyl Lithium, poly-1,3-cyclohexadienyllithium, polystyrene-1,3-cyclohexadienyllithium, polybutadiene-1,3-cyclohexadienyllithium.

Among these, n-butyllithium, second butyllithium, tert-butyllithium, 1,3-phenylene-bis-(3-methyl-1-phenylpentylene)dilithium are preferred. .

Conjugated Diene Compound

In the above polymerization reaction, examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. , 2-methyl-1,3-octadiene, 1,3-hexadiene, 1,3-cyclohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl Base - 1,3-octadiene, myrcene, chloroprene. Among these, 1,3- Butadiene and isoprene are preferred because of their high polymerization reactivity and their ease of industrial availability. The conjugated diene compounds may be used alone or in combination of two or more.

Other Monomers

In the above polymerization reaction, another monomer such as an aromatic alkenyl compound may be used together with the conjugated diene compound. Examples of the other monomer include an unsaturated monomer having a specific group and an unsaturated monomer having no specific group. In the above polymerization reaction, when a unsaturated monomer having a specific group is used, it corresponds to the method of the above [B].

The ratio of the content of the aromatic alkenyl compound unit and the conjugated diene compound unit in the conjugated diene block copolymer A (aromatic alkenyl compound unit / conjugated diene compound unit) is usually a mass ratio, usually It is 0/100~80/20, preferably 3/97~60/40. These contents are determined by infrared absorption spectroscopy (Morello method).

The unsaturated monomer having a specific group can be reacted with the active site of the block copolymer obtained by the above polymerization. In this case, it corresponds to the method of the above [E]. If it is relative to the number of moles of the active point derived from the organic alkali metal, it is usually 0.01 times moles to 100 times moles, preferably 0.01 times moles to 10 times moles, and particularly preferably 1.0 times moles. It is preferable in this respect that the ratio of 3.0 times moles is added to the unsaturated monomer having a specific group, and the side reaction is small.

The other monomers may be used alone or in combination of two or more.

Unsaturated monomer with specific groups

Examples of the unsaturated monomer having a specific group (the group represented by the formula (i) to the formula (iii)) include an aromatic alkenyl compound represented by the formula (2), and (meth) Bis(trimethyldecyl)aminomethyl acrylate, bis(trimethyldecyl)aminoethyl (meth)acrylate.

Formula (2), a group represented by the formula X represents (i) or formula (ii), R ⁷ represents a direct bond or alkylene group having a carbon number of 1 to 20 carbon atoms or an alkylene group having 1 to 20, more Preferably, it represents an alkylene group having 1 to 20 carbon atoms; and n represents an integer of 1 to 3, preferably an integer of 1 to 2.

The unsaturated monomer represented by the formula (2) is, for example, p-[N,N-bis(trimethylsilyl)amino]styrene (p-[N,N-bis(trimethylsilyl)amino]styrene). For [N,N-bis(trimethyldecyl)aminomethyl]styrene, p-[2-{N,N-bis(trimethyldecyl)amino}ethyl]styrene, [N,N-bis(trimethyldecyl)amino]styrene, m-[N,N-bis(trimethyldecyl)aminomethyl]styrene, inter-[2-{N,N- Bis(trimethyldecyl)amino}ethyl]styrene, o-[N,N-bis(trimethyldecyl)amino]styrene, o-[N,N-bis(trimethyldecyl) Aminomethyl]styrene, o-[2-{N,N-bis(trimethyldecyl)amino) Ethyl]styrene, p-[N-(t-butyl-dimethylalkyl)-N-trimethyldecylamino]styrene, p-[N-(t-butyl-dimethyldecane) -N-trimethyldecylaminomethyl]styrene, p-[2-{N-(t-butyl-dimethyldecyl)-N-trimethyldecylalkylamino}ethyl ]]styrene, p-[N-{bis(tert-butyl)-methyldecyl}}-N-trimethyldecylamino]styrene, p-[N-{di(t-butyl)-- Base alkyl}-N-trimethyldecylaminomethyl]styrene, p-2-[N-{bis(tert-butyl)-methyldecyl}}-N-trimethyldecylalkylamino Ethylstyrene, o-[N-(t-butyl-dimethylalkylalkyl)-N-trimethyldecylalkylamino]styrene, o-[N-(t-butyl-dimethyldecane) -N-trimethyldecylaminomethyl]styrene, o-[2-{N-(t-butyl-dimethyldecyl)-N-trimethyldecylalkylamino}ethyl ]styrene, o-[N-{di(t-butyl)-methyldecyl}}-N-trimethyldecylamino] styrene, o-[N-{di(t-butyl)-- Base alkyl}-N-trimethyldecylaminomethyl]styrene, o-[N-{bis(t-butyl)-methyldecyl}}-N- Alkylamino]ethylstyrene, m-[N-(t-butyl-dimethylalkylalkyl)-N-trimethyldecylalkylamino]styrene, m-[N-(t-butyl -Dimethyldecyl)-N-trimethyldecylalkylaminomethyl]styrene, m-[2-{N-(t-butyl-dimethylmethyl)-N-trimethyldecyl Amino}ethyl]styrene, m-[N-{bis(t-butyl)-methyldecyl}}-N-trimethyldecylamino]styrene, inter-[N-{two (third Butyl)-methyldecyl}}-N-trimethyldecylaminomethyl]styrene, m-[N-{bis(t-butyl)-methyldecyl}-N-trimethyl An aromatic alkenyl compound having a group represented by the formula (i), such as an alkylamino]ethylstyrene; p-(N-methyl-N-trimethyldecylalkylamino)styrene, p-( N-methyl-N-trimethyldecylalkylaminomethyl)styrene, p-[2-(N-methyl-N-trimethyldecylalkylamino) Ethyl]styrene, m-(N-methyl-N-trimethyldecylamino)styrene, m-(N-methyl-N-trimethyldecylaminomethyl)styrene, inter 2-(N-methyl-N-trimethyldecylamino)ethyl]styrene, o-(N-methyl-N-trimethyldecylalkylamino)styrene, o-(N-methyl -N-trimethyldecylaminomethyl)styrene, o-[2-(N-methyl-N-trimethyldecylamino)ethyl]styrene, p-[N-(third -dimethyl dimethylalkyl)-N-methylamino] styrene, p-{{N-(t-butyl-dimethyl decyl)-N-methylamino}methyl] styrene, [2-{N-(Tertiary butyl-dimethyldecyl)-N-methylamino}ethyl]styrene, p-[{N-bis(t-butyl)-methyldecylalkyl -N-methyl}amino]styrene, p-{{N-bis(t-butyl)-methyldecyl-N-methyl}aminomethyl]styrene, p-[N-di( Tert-butyl)-methyldecyl-N-methyl}aminoethyl]styrene, o-[N-(t-butyl-dimethylmethyl)-N-methylamino]styrene , o-[{N-(T-butyl-dimethylalkylalkyl)-N-methylamino}methyl]styrene, o-[2-{N-(t-butyl-dimethyldecyl) )-N-methylamino group }ethyl]styrene, o-[{N-bis(t-butyl)-methyldecyl-N-methyl}amino]styrene, o-[{N-bis(t-butyl)-- Alkyl-N-methyl}aminomethyl]styrene, o-[{N-bis(t-butyl)-methyldecyl-N-methyl}aminoethyl]styrene, inter N-(t-butyl-dimethyldecyl)-N-methylamino]styrene, m-[{N-(t-butyl-dimethylalkyl)-N-methylamino} Methyl]styrene, m-[2-{N-(t-butyl-dimethyldecyl)-N-methylamino}ethyl]styrene, inter-[{N-di(t-butyl) )-methylalkylalkyl-N-methyl}amino]styrene, m-[{N-bis(t-butyl)-methyldecyl-N-methyl}aminomethyl]styrene, An aromatic alkenyl compound having a group represented by the formula (ii), such as {{N-bis(t-butyl)-methyldecyl-N-methyl}aminoethyl]styrene.

Among these, preferably [N,N-bis(trimethyldecyl)amino]styrene, p-[N,N-bis(trimethyldecyl)aminomethyl]styrene, pair [2-{N,N-bis(trimethyldecyl)amino}ethyl]styrene.

Unsaturated monomer without specific group

Examples of the unsaturated monomer having no specific group include styrene, t-butyl styrene, α-methyl styrene, p-methyl styrene, p-ethyl styrene, divinyl benzene, and 1,1. -diphenylethylene, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-vinylindole, 9-vinylindole, p-vinylbenzylpropyl ether, p-vinylbenzylbutyl ether, ethylene Benzyl hexyl ether, p-vinylbenzyl pentyl ether, m-N-N-diethylaminoethyl styrene, p-N,N-diethylaminoethyl styrene, N,N- Dimethylaminoethylstyrene, o-vinylbenzyldimethylamine, p-vinylbenzyldimethylamine, p-vinylbenzyldiethylamine, p-vinylbenzyldi(n-propyl) An aromatic alkenyl compound such as an amine, p-vinylbenzyl di(n-butyl)amine, vinylpyridine, 2-vinylbiphenyl or 4-vinylbiphenyl.

Among these, styrene and t-butyl styrene are industrially easy to obtain because of high polymerization reactivity, and the hydrogenated conjugated diene block copolymer C finally obtained has good moldability and is preferable.

Polymerization Stopper

In the above polymerization, in the case where the obtained block copolymer has an active site, it is usually preferred to inactivate the active site by using a polymerization stopper. Examples of the polymerization stopper include a polymerization stopper having a specific group and a polymerization stopper having no specific group.

The polymerization stoppers may be used alone or in combination of two or more.

Polymerization stopper with specific base

The polymerization stopper having a specific group (the group represented by the formula (i) to the formula (iii)) may, for example, be a decane compound having a specific group, particularly a decane compound represented by the formula (3). When a polymerization stopper having a specific group is used, it corresponds to the method of the above [C].

R ⁸ _(4-mn) Si(OR ⁹ ) _m X _n (3)

In the formula (3), R ⁸ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an organodecyloxy group having 1 to 100 carbon atoms. It is an alkyl group having 1 to 20 carbon atoms. In the case when there are a plurality of R ^8, each R ⁸ may be the same group may also be different groups. R ⁹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms. In the case when there are a plurality of R ^9, R ⁹ may be each the same group may also be different groups.

X is a group represented by the formula -A-X' (wherein, A is an alkylene group having 1 to 20 carbon atoms, and X' is a group represented by the formula (i) to the formula (iii)). In the case where there are multiple Xs, each X may be the same group or a different group.

m is 1, 2 or 3, and n is 1, 2 or 3.

The sum of m and n is an integer of 2 to 4.

The amount of the polymerization stopper having a specific group used in the reaction with the active point of the block copolymer is usually 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol, relative to the block copolymer. %the above. In addition, although the amount of the polymerization stopper depends on the molecular weight of the polymerization stopper, it is usually relative to the block copolymer. It is 0.001% by mass or more, preferably 0.01% by mass or more, and more preferably 0.02% by mass or more. By setting it as this range, the affinity of the hydrogenated conjugated diene block copolymer C finally obtained, and various polymers, a filler, etc. can fully be improved.

The decane compound represented by the formula (3) may, for example, be N,N-bis(trimethyldecyl)aminoethyltrimethylnonane or N,N-bis(trimethyldecyl)amino group B. Triethoxy decane, N,N-bis(trimethyldecyl)aminoethyl methoxy decane, N,N-bis(trimethyldecyl)aminoethyl dimethyl Ethoxy decane, N,N-bis(trimethyldecyl)aminoethyldimethoxydecane, N,N-bis(trimethyldecyl)aminoethylmethyldiethoxylate Baseline, N,N-bis(trimethyldecyl)aminopropyltrimethoxydecane, N,N-bis(trimethyldecyl)aminopropyltriethoxydecane, N,N- Bis(trimethyldecyl)aminopropyldimethylmethoxydecane, N,N-bis(trimethyldecyl)aminopropyldimethylethoxydecane, N,N-bis ( Trimethyldecyl)aminopropylmethyldimethoxydecane, N,N-bis(trimethyldecyl)aminopropylmethyldiethoxydecane, N-trimethyldecyl- N-(dimethyl-t-butyldecyl)aminoethyltrimethoxydecane, N-trimethyldecyl-N-(dimethyl-t-butyldecyl)aminoethyl Ethoxy decane, N- Methyl decyl-N-(dimethyl-t-butyldecyl)aminoethyl methoxy decane, N-trimethyldecyl-N-(dimethyl-t-butyl矽alkyl)aminoethyl dimethyl ethoxy decane, N-trimethyl-N-(dimethyl decyl-t-butyl decyl) aminoethyl dimethoxy decane, N -trimethyldecyl-N-(dimethyl-t-butyldecyl)aminoethyldiethoxydecane, N-trimethyldecyl-N-(dimethyl-third Butyl decyl)aminopropyltrimethoxydecane, N-trimethyldecyl-N-(dimethyl- Tert-Butylalkyl)aminopropyltriethoxydecane, N-trimethyldecyl-N-(dimethyl-t-butyldecyl)aminopropyldimethylmethoxydecane , N-trimethyldecyl-N-(dimethyl-t-butyldecyl)aminopropyldimethylethoxydecane, N-trimethyldecyl-N-(dimethyl- Tert-Butylalkyl)aminopropylmethyldimethoxydecane, N-trimethyldecyl-N-(dimethyl-t-butyldecyl)aminopropylmethyldiethoxy Baseline, N-N', N'-tris(trimethyldecyl)-N-(2-aminoethyl)-3-aminoethyltrimethoxydecane, N-N', N'- Tris(trimethyldecyl)-N-(2-aminoethyl)-3-aminoethyltriethoxydecane, N-N',N'-tris(trimethyldecyl)-N -(2-Aminoethyl)-3-aminoethylmethyldimethoxydecane, N-N',N'-tris(trimethyldecyl)-N-(2-aminoethyl --3-aminoethylmethyldiethoxydecane, N-N', N'-tris(trimethyldecyl)-N-(2-aminoethyl)-3-aminoethyl Dimethyl methoxydecane, N-N', N'-tris(trimethyldecyl)-N-(2-aminoethyl)-3-aminoethyl dimethyl ethoxy decane, N-N', N'-tris(trimethylhydrazine) -N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-N',N'-tris(trimethyldecyl)-N-(2-aminoethyl 3-amino-3-trimethoxydecane, N-N', N'-tris(trimethyldecyl)-N-(2-aminoethyl)-3-aminopropyl Dimethoxy decane, N-N', N'-tris(trimethyldecyl)-N-(2-aminoethyl)-3-aminopropylmethyldiethoxydecane, N -N',N'-tris(trimethyldecyl)-N-(2-aminoethyl)-3-aminopropyldimethylmethoxydecane, N-N', N'-three (Trimethyldecyl)-N-(2-aminoethyl)-3-aminopropyldimethylethoxydecane, N,N',N",N"-tetrakis(trimethyldecane -N'-(2-Aminoethyl)-N-(2-aminoethyl)-3-aminoethyltrimethoxydecane, N,N',N",N"-tetra Trimethyl decane -N'-(2-Aminoethyl)-N-(2-aminoethyl)-3-aminoethyltriethoxydecane, N,N',N",N"-four (trimethyldecyl)-N'-(2-aminoethyl)-N-(2-aminoethyl)-3-aminoethylmethyldimethoxydecane, N,N', N",N"-tetrakis(trimethyldecyl)-N'-(2-aminoethyl)-N-(2-aminoethyl)-3-aminoethylmethyldiethoxy矽, N, N', N", N"-tetrakis(trimethyldecyl)-N'-(2-aminoethyl)-N-(2-aminoethyl)-3-amino Dimethyl methoxy decane, N, N', N", N"-tetrakis(trimethyldecyl)-N'-(2-aminoethyl)-N-(2-aminoethyl )-3-aminoethyldimethylethoxydecane, N,N',N",N"-tetrakis(trimethyldecyl)-N'-(2-aminoethyl)-N- (2-Aminoethyl)-3-aminopropyltrimethoxydecane, N,N',N",N"-tetrakis(trimethyldecyl)-N'-(2-aminoethyl )-N-(2-Aminoethyl)-3-aminopropyltriethoxydecane, N,N',N",N"-tetrakis(trimethyldecyl)-N'-(2 -aminoethyl)-N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N,N',N",N"-tetrakis(trimethyldecylalkyl) )-N'-(2-Aminoethyl)-N-(2-aminoethyl)-3-aminopropylmethyldiethoxydecane, N,N',N",N"- (Trimethyldecyl)-N'-(2-aminoethyl)-N-(2-aminoethyl)-3-aminopropyldimethylmethoxydecane, N,N', N",N"-tetrakis(trimethyldecyl)-N'-(2-aminoethyl)-N-(2-aminoethyl)-3-aminopropyldimethylethoxy a decane compound having a group represented by the formula (i) such as decane; N-methyl-N-trimethyldecylaminopropyltrimethoxydecane, N-methyl-N-trimethyldecylamine Propyltriethoxydecane, N-methyl-N-trimethyldecylaminopropyldimethylethoxydecane, N-methyl-N-trimethyldecylalkylaminopropyl Methyl methoxy decane, N-methyl-N-trimethyl decylaminopropyl propyl methyl diethoxy decane, N-methyl-N-trimethyl decylaminopropyl propyl methyl Methoxydecane, N-methyl -N-trimethyldecylaminoethyltrimethoxydecane, N-methyl-N-trimethyldecylaminoethyltriethoxydecane, N-methyl-N-trimethyldecane Aminoethyl dimethyl ethoxy decane, N-methyl-N-trimethyl decylalkylaminoethyl methoxy decane, N-methyl-N-trimethyl decylamine a decane compound having a group represented by the formula (ii), such as ethyl ethyl methyl diethoxy decane or N-methyl-N-trimethyl decylaminoethyl methyl dimethoxy decane; -(3-trimethoxydecylethyl)-2,2,5,5-tetramethyl-1-aza-2,5-didecylcyclopentane (1-(3-trimethoxysilylethyl)-2 , 2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane), 1-(3-triethoxydecylethyl)-2,2,5,5-tetramethyl-1-nitrogen Hetero-2,5-dihalogenated cyclopentane, 1-(3-trimethyldimethoxydecylethyl)-2,2,5,5-tetramethyl-1-aza-2, 5-dioxocyclopentane, 1-(3-trimethyldiethoxydecylethyl)-2,2,5,5-tetramethyl-1-aza-2,5-diindole Cyclopentane, 1-(3-tris-dimethylmethoxydecylethyl)-2,2,5,5-tetramethyl-1-aza-2,5-diindolecyclopentyl Alkane, 1-(3-tri-dimethylethoxy)矽alkylethyl)-2,2,5,5-tetramethyl-1-aza-2,5-diindolecyclopentane, 1-(3-trimethoxydecylpropyl)-2, 2,5,5-tetramethyl-1-aza-2,5-diindole cyclopentane, 1-(3-triethoxydecylpropyl)-2,2,5,5-tetra Methyl-1-aza-2,5-diindole cyclopentane, 1-(3-trimethyldimethoxydecylpropyl)-2,2,5,5-tetramethyl-1 -aza-2,5-dihalocyclopentane, 1-(3-trimethyldiethoxydecylpropyl)-2,2,5,5-tetramethyl-1-aza- 2,5-dihalocyclopentane, 1-(3-tris-dimethylmethoxydecylpropyl)-2,2,5,5-tetramethyl-1-aza-2,5 -diodescyclopentane, 1-(3-tris-dimethylethoxydecylpropyl)-2,2,5,5-tetramethyl-1-aza-2,5-diindole Cyclopentyl A decane compound having a group represented by the formula (iii) such as an alkane.

Among these, N,N-bis(trimethyldecyl)aminopropyltrimethoxydecane, N,N-bis(trimethyldecyl)aminopropylmethyldimethoxy is preferred. Decane, N,N-bis(trimethyldecyl)aminopropylmethyldiethoxydecane, N-methyl-N-trimethyldecylaminopropylmethyldiethoxydecane, 1-(3-Triethoxydecylpropyl)-2,2,5,5-tetramethyl-1-aza-2,5-diindolecyclopentane.

Polymerization stop agent without specific base

Examples of the polymerization stopper which does not have a specific group include hydrogen; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, and octanol; Alkane, chlorinated propane, butane chloride, benzyl chloride, methyl bromide, ethane bromide, propane bromide, butane bromide, methane iodide, ethane iodide, propidium iodide, iodine iodide An alkyl halide such as an alkane.

Among these, hydrogen is preferred.

Coupler

By reacting a coupling agent having a specific group with a polymerization terminal at a time when the polymerization is substantially completed, a specific group can be introduced into the polymer at the same time as the coupling reaction. In the coupling reaction, the reaction temperature is usually from 0 ° C to 120 ° C, preferably from 50 ° C to 100 ° C, and the reaction time is usually from 1 minute to 30 minutes, preferably from 5 minutes to 20 minutes.

The coupling agents may be used alone or in combination of two or more.

Coupler with specific base

Examples of the coupling agent having a specific group include N,N-bis(trimethyldecyl)aminopropyltrichlorodecane, and N,N-bis(trimethyldecyl)aminopropylmethyldichloride. Decane, 1-(3-trichlorodecylalkyl)-2,2,5,5-tetramethyl-1-aza-2,5-diindolecyclopentane, 1-(3-methyl Dichlorodecylpropyl)-2,2,5,5-tetramethyl-1-aza-2,5-diindolecyclopentane.

Coupler without specific base

Examples of the coupling agent having no specific group include a halogen compound, an epoxy compound, a carbonyl compound, and a polyvinyl compound. Specific examples of the above coupling agent include methyl dichlorodecane, methyl trichlorodecane, butyl trichlorodecane, tetrachlorodecane, dibromoethane, epoxidized soybean oil, divinylbenzene, tetrachlorotin, and butyl. Trichlorotin, tetrachloropurine, bis(trichlorodecanealkyl)ethane, diethyl adipate, dimethyl adipate, dimethyl terephthalic acid, diethyl terephthalic acid, polyisocyanate .

"Composition of polymer blocks"

The conjugated diene block copolymer A may be obtained by block-polymerizing a conjugated diene compound or a conjugated diene compound with another monomer such as an aromatic alkenyl compound, but the obtained composition is The conjugated diene block copolymer A is preferably one or more polymer blocks having a polymer block selected from the following (A) to (D) in terms of physical properties and moldability. Block copolymer.

(A) An aromatic alkenyl polymer block in which the amount of the aromatic alkenyl compound unit is 80% by mass or more.

(B) A conjugated diene polymer block having a conjugated diene compound unit amount of 80% by mass or more and a total of 1,2 bond content and a 3,4 bond content of less than 30 mol%.

(C) a conjugated diene polymer unit having an amount of a conjugated diene compound of 80% by mass or more and a total of 1, 2, and 3, 4 bonds in a total amount of 30 mol% to 90 mol% segment.

(D) A random copolymer block of a conjugated diene compound and an aromatic alkenyl compound in an amount of the conjugated diene compound unit of more than 20% by mass and less than 80% by mass.

When the polymer block is a copolymer block formed of two or more kinds of compounds, a random type, or an aromatic alkenyl compound unit or a conjugated diene compound unit can be produced according to the purpose of the resin composition. The so-called taper type in which the content continuously changes in the polymer block.

The above-mentioned "block copolymer having two or more polymer blocks selected from the polymer blocks of (A) to (D)" may, for example, be (A)-(B), (A)- (C), (A)-(D), (B)-(C), (B)-(D), [(A)-(B)]xY, [(A)-(C)]xY, [(A)-(D)]xY, [(B)-(C)]xY, [(B)-(D)]xY, [(B)-(A)]xY, [(C)-( A)]xY, [(D)-(A)]xY, (A)-(B)-(D), (A)-(B)-(A), (A)-(C)-(A ), (A)-(C)-(B), (A)-(D)-(A), (B)-(A)-(B), (B)-(C)-(B), [(A)-(B)-(D)]xY, [(A)-(B)-(A)]xY, [(A)-(C)-(A)]xY, [(A)- (C)-(B)]xY, [(A)-(D)-(A)]xY, [(B)-(A)-(B)]xY, (A)-(B)-(A )-(B), (B)-(A)-(B)-(A), [(A)-(B)-(A)-(B)]xY, (A)-(B)-( A)-(B)-(A), [(A)-(B)-(A)-(B)-(A)]xY, (B)-(A)-(B)-(D), (B)-(A)-(B)-(A), (B)-(A)-(C)-(A), (B)-(A)-(C)-(B), (B )-(A)-(D)-(A), [(C)-(A)-(B)-(D)]xY, [(C)-(A)-(B)-(A)] xY, [(C)-(A) -(C)-(A)]xY, [(C)-(A)-(C)-(B)]xY, [(C)-(A)-(D)-(A)]xY, ( C)-(A)-(B)-(A)-(B), (C)-(B)-(A)-(B)-(A), (C)-(A)-(B) -(A)-(C), [(C)-(A)-(B)-(A)-(B)]xY, (C)-(A)-(B)-(A)-(B )-(A), [(C)-(A)-(B)-(A)-(B)-(A)]xY (where x≧2, Y is the residue of the coupling agent). In the case of forming a pellet shape, it is preferred to have at least one selected from the group consisting of the polymer block (A) and the polymer block (B) as the outer side of the conjugated diene block copolymer. Segment component.

In the present specification, the content of the vinyl bond means a conjugated diene compound unit which is incorporated in a bond pattern of a 1, 2 bond, a 3, 4 bond, and a 1, 4 bond in a polymer block before hydrogenation. The total ratio (mol% basis) of the units incorporated by the 1, 2 and 3, 4 bonds. The vinyl bond content (1, 2 bond content and 3, 4 bond content) can be determined by infrared absorption spectroscopy (Morello method).

The micro structure of the conjugated diene block copolymer A, that is, the 1,2 bond content and the 3,4 bond content can be controlled by using a Lewis base together with the above hydrocarbon solvent.

Examples of the Lewis base include ethers and amines, and specific examples thereof include diethyl ether, tetrahydrofuran, propyl ether, butyl ether, 2,2-bis(tetrahydrofuranyl)propane, higher ether, and tetrahydrofurfuryl methyl ether. , tetrahydrofurfuryl ethyl ether, 1,4-dioxane, bis (tetrahydrofurfuryl) formal, 2,2-bis(2-tetrahydrofurfuryl)propane, An ether derivative of a polyalkylene glycol such as ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, propylene glycol diethyl ether or propylene glycol ethyl propyl ether; tetramethylethylenediamine, pyridine, tributylamine A tertiary amine.

In the polymer block (D), the "random copolymer block of a conjugated diene compound and an aromatic alkenyl compound" means a single-chain aromatic alkenyl unit (that is, two or more aromatic groups). The aromatic alkenyl unit in the case where the alkenyl unit is discontinuous is irregularly present in the polymer block B.

Here, in the case where the aromatic alkenyl compound unit is a styrene unit, the state in which the single-chain styrene unit is irregularly present in the polymer block B is determined by the random styrene content as follows.

The structural analysis of the obtained block copolymer X and the polymer composition was carried out by using ¹ H-NMR spectrum at 500 MHz using deuterated chloroform as a solvent. By structural analysis, the state of the styrene chain was determined from the integral value (S') of the following range, and the random styrene content was set as the integral value of the following a) with respect to the points a) to c) described below. The ratio of the total value of the value.

a) Styrene single chain: 8.00 ppm≦S≦6.89 ppm

b) Styrene chain 2~7: 6.89 ppm<S≦6.68 ppm

c) styrene chain 8 or more: 6.68 ppm<S≦6.00 ppm

[Resin composition]

The hydrogenated conjugated diene block copolymer C of the present invention is excellent in stability over time, and is excellent in the modification effect of a resin or a resin composition, and is excellent in compatibility effects of the conventional different types of polymer mixtures. Therefore, by using a resin composition containing the hydrogenated conjugated diene block copolymer C of the present invention and other polymers, workability, heat resistance, rigidity, impact resistance, surface impact resistance, and stretching can be formed. A molded article excellent in balance between elongation at break, specularity, and interlayer peelability.

The resin composition of the present invention contains at least one group selected from the group represented by the formula (i), the group represented by the formula (ii), and the group represented by the formula (iii), and the above decane a hydrogenated conjugated diene block copolymer having a base protection ratio of 70% or more (hereinafter also referred to as "component (I)"); and a non-polar polymer (hereinafter also referred to as "component (II-1)) ") At least one of a polar polymer (hereinafter also referred to as "component (II-2)") and a filler (hereinafter also referred to as "component (III)"). Among them, the polar polymer (ingredient (II-2)) does not contain the above hydrogenated conjugated diene block copolymer (ingredient (I)). As the hydrogenated conjugated diene block copolymer, the hydrogenated conjugated diene block copolymer C obtained by the above method can be used.

The non-polar polymer and the polar polymer may be a resin or a rubber.

<Component (II-1)>

Component (II-1) is preferably a polyolefin polymer and an aromatic alkenyl polymer.

Examples of the polyolefin polymer include: Very Low Density PolyEthylene (VLDPE), Linear Low Density PolyEthylene (LLDPE), Low Density PolyEthylene (LDPE), and medium density. Polyethylene resin such as polyethylene (Medium Density PolyEthylene, MDPE), High Density PolyEthylene (HDPE); polypropylene resin (PolyPropylene, PP) of random type, block type or homotypic; - Ethylene-Propylene polymer (EPM), Ethylene-1-Butene polymer (EBM), ethylene-hexene copolymer (Ethylene-Hexene polymer, EHM), Ethylene-Octene polymer (EOM) and other copolymers of ethylene and 3 to 20 alpha-olefins; propylene-1-butene copolymer (Propylene-1-Butene polymer, PBM) and other copolymers of propylene and α-olefin having 4 to 20 carbon atoms; Ethylene-Propylene-1-Butene polymer (EPBM) Ethylene-Propylene-Diene polymer (EPDM), ethylene-1-butene-diene polymer (EBDM), etc. Copolymer; poly-1-Butene (PB), polymethylpentene (PMP), polybutadiene (PBD). These may be used alone or in combination of two or more.

Examples of the aromatic alkenyl polymer include General Purpose Polystyrene (GPPS), High Impact Polystyrene (HIPS), isotactic Polystyrene (iPS), and Polystyrene resin such as syndiotactic polystyrene (sPS) or poly-α-methylstyrene (PαMS). These may be used alone or in combination of two or more.

<Component (II-2)>

The component (II-2) is, for example, preferably a polymer having at least one functional group selected from the group consisting of a carboxyl group (including a carboxyl group forming an acid anhydride or a metal salt), a hydroxyl group, a halogen group, an epoxy group, and an oxazole. a phenyl group, a sulfonic acid group, an isocyanate group, a thiol group, a group having an ester bond, a group having a carbonate bond, a group having a guanamine bond, A group having an ether bond, a group having a urethane bond, and a group having a urea bond.

Examples of the polymer having the above functional group include Ethylene Acrylic Acid (EAA), Ethylene Methacrylic Acid (EMA), and ethylene-maleic anhydride-(methyl). Acrylic acid copolymer, ethylene-ethyl (meth) acrylate-maleic anhydride copolymer, ethylene (meth) and (meth) derived from structural units of (meth)acrylic acid in an amount of 7 mol% to 15 mol% a copolymer of acrylic acid, and a carboxyl group-containing polymer such as an ionomer (Ionomer, IO) having a degree of neutralization of metal ions of Na, Zn, Mg or the like; polyethylene terephthalate (PolyEthylene) Terephthalate, PET), PolyButylene Terephthalate (PBT), PolyEthylene Naphthalate (PEN), Poly Lactic Acid (PLA), Polyhydroxyalkanoic (PolyHydroxyalkanoic) Acid, PHA), polylactone, polycaprolactone, polyethylene succinate, polybutyl succinate, polyethylene adipate, polybutylene polysuccinate Succinate adipate) and other polyester resins; nylon 4,6 (PA46 ), nylon 6 (PA6), nylon 6,6 (PA66), nylon 6,10 (PA610), nylon 6,12 (PA612), nylon 12 (PA12), nylon 6, T (PA6T), nylon 9, T (PA9T), reinforced polyamine, polyammonium resin (PolyAmide, PA) modified by polymethylene phthalate formed from hexamethylenediamine and terephthalic acid; ethylene-methyl acrylate copolymer (Ethylene) -MethylAcrylate, EMA), Ethylene-Ethyl Acrylate, EEA), ethylene-isopropyl acrylate copolymer, ethylene-ethyl 2-ethylhexyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene -Isobutyl methacrylate copolymer, ethylene-butyl methacrylate copolymer, Ethylene-HydroxyEthyl Methacrylate (HEMA), ethylene-methacrylic acid-2- Hydroxypropyl ester copolymer, ethylene-aminoalkyl methacrylate copolymer, Ethylene-Glycidyl Methacrylate (EGMA), polymethyl methacrylate (PolyMethyl Methacrylate) , PMMA), PolyEthyl Methacrylate (PEMA), Methacrylic Styrene Resin (MS Resin) and other acrylic polymers; poly-2,2-bis(hydroxybenzene) Polycarbonate such as propane carbonate (PolyCarbonate, PC); poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4 -phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether) Polyphenylene ether (PPE), PolyVinyl Acetate (PVAc), Liquid Crystal Polyester (LCP), modified polyphenylene ether (PPE) Polyacetal-polystyrene (POM), Acrylonitrile-Butadiene-Styrene (ABS) resin, Acrylonitrile-Ethylene-Styrene (AES) resin, acrylonitrile- Acrylonitrile-Styrene-Acrylate (ASA) resin, Ethylene-Vinyl Acetate (EVA) resin, B Ethylene-vinyl propionate copolymer, diallyl phthalate resin (Diallyl Phthalate, DAP), phenolic resin (PF), polyvinyl alcohol (PolyVinylAlcohol, PVA), ethylene-vinyl alcohol copolymerization Ethylene-Vinylalcohol copolymer (EVOH), Polyarylate (PAR), Norbornene resin, Polyethylene oxide, Polyphenylene Sulfide (PPS), Polysulfone (PSU) Polyethersulfone (PES); thermoplastic polyester elastomer (elastomer), thermoplastic polyurethane elastomer, thermoplastic polyamide elastomer, α,β-unsaturated nitrile-acrylate-unsaturated Diene copolymer rubber, urethane rubber, chloroprene rubber, bromobutane rubber, acrylic rubber, ethylene-acrylic rubber, epichlorohydrin rubber, epichlorohydrin-ethylene oxide Rubber, chloroprene rubber; chlorosulfonated polyethylene, chlorinated polyethylene, chlorinated polypropylene, oxazoline modified polystyrene, oxazoline modified styrene-acrylonitrile copolymer. These may be used alone or in combination of two or more.

In the polymer of the component (II-1) and the component (II-2), a polyethylene resin having a structural unit derived from ethylene, a polypropylene resin having a structural unit derived from propylene, and an aromatic olefin derived from the aromatic olefin are exemplified. Polystyrene resin of structural unit of the base compound, polyester resin such as polylactic acid and polyethylene terephthalate, polyamine resin, acrylic polymer, ethylene-vinyl alcohol copolymer due to component (I) The molecular chain structure is excellent in physical property improvement, and can be widely used for use.

The polymer which is exemplified as the component (II-1) and the component (II-2) may be a synthetic resin using a monomer derived from biomass.

When the resin composition of the present invention contains the component (I) and the component (II-1), or when the component (I) and the component (II-2) are contained, the resin composition may be set to the following content ratio. In other words, when the component (II-1) and the component (II-2) are expressed as "component (II)", the component (I) / component (II) (mass ratio) is preferably from 1 to 99/99 to 1 More preferably, it is 5~95/95~5, and then 10~90/90~10.

When the resin composition of the present invention contains the component (I), the component (II-1), and the component (II-2), the following content ratio can be set. That is, the component (II-1) / component (II-2) (mass ratio) is preferably from 1 to 99/99 to 1, more preferably from 5 to 95/95 to 5, and further preferably from 10 to 90/90. When the content of the component (II-1) and the component (II-2) is 100 parts by mass, the content of the component (I) is preferably from 1 part by mass to 100 parts by mass, more preferably 5 parts by mass to 50 parts by mass, and more preferably 10 parts by mass to 40 parts by mass.

<Component (III)>

Examples of the component (III) include magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, calcium hydroxide, barium hydroxide, basic magnesium carbonate, dolomite, hydrotalcite, tin oxide, and titanium oxide. , zinc oxide, iron oxide, magnesium oxide, aluminum oxide, barium sulfate, calcium sulfate, sodium sulfate, calcium sulfite, calcium citrate, calcium carbonate, magnesium carbonate, phosphate compounds, carbon, glass beads, glass powder, asbestos ( Asbest), mica, talc, cerium oxide, zeolite, kaolin, cerium, vermiculite, quartz powder, white sand, metal fiber and other inorganic fibers, potassium titanate whiskers and other inorganic whiskers. The order Use one type or two or more types in combination.

The component (III) can be used as it is without being treated, but in order to improve affinity with various polymers or interfacial bonding force, etc., it is also possible to use a surface treatment agent using a fatty acid (for example, stearic acid or oleic acid). , palmitic acid) or a metal salt thereof, a paraffin wax, a wax, a polyethylene wax or the like, an organoborane, an organic titanate, a decane coupling agent, an aluminum coupling agent, and the like.

Among these, those used as the flame retardant include, for example, magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, calcium hydroxide, barium hydroxide, basic magnesium carbonate, dolomite, hydrotalcite, and tin oxide. Among these, magnesium hydroxide, aluminum hydroxide, and calcium hydroxide are preferable and are industrially easy to obtain, and thus are preferable. Magnesium hydroxide has a high flame retardant effect and is particularly excellent.

In addition, in the case of using a flame retardant, in order to improve the flame retardant effect, a phosphorus-based flame retardant such as a red phosphorus-based flame retardant, an ammonium polyphosphate-based flame retardant or a phosphate ester, a polysiloxane compound, or a quartz may be used in combination. Water glass such as glass or the like as a flame retardant auxiliary agent for preventing frit or drip of tantalum nitride short fibers.

When the total amount of the polymer components such as the component (I) and the component (II) is 100 parts by mass, the content of the component (III) is preferably from 1 part by mass to 90 parts by mass, more preferably from 2 parts by mass to 80 parts by mass. Parts by mass. When the content of the component (III) is within the above range, the effects of the component (I), the component (II-1) and the component (II-2) are not impaired, and properties such as flame retardancy and strength can be imparted.

<Other ingredients>

In the resin composition of the present invention, in addition to the above components, the following components may be blended as other additives: an anti-aging agent, a weathering agent, a metal passivating agent, and a light stable Stabilizers such as fixatives, ultraviolet absorbers, heat stabilizers, antibacterial/mold inhibitors, dispersants, softeners, plasticizers, crosslinkers, co-crosslinkers, vulcanizing agents, vulcanization aids, foaming agents Metal foams such as foaming aids, coloring agents, ferrites, organic fibers such as carbon fibers and aromatic polyamide fibers, and composite fibers. In addition, it can also be equipped with graphite, pumice, ebonite powder, cotton flock, cork powder, fluororesin, polymer bead, polyolefin wax, Cellulose powder, rubber powder, low molecular weight polymer, and the like. In the case of crosslinking, the method is not particularly limited, and examples thereof include sulfur crosslinking, peroxide crosslinking, electron beam crosslinking, ultraviolet crosslinking, radiation crosslinking, metal ion crosslinking, decane crosslinking, and resin. Cross-linking and so on. In addition, the foaming agent will be described together with the description of foam molding.

<Manufacture of Resin Composition>

In the production of the resin composition of the present invention, a conventionally known kneading machine such as an extruder, a pressure kneader, or a Banbury mixer, and a kneading machine in which these are combined may be used. In the case of kneading, each component may be kneaded together, or a multi-stage split kneading method in which the remaining components are kneaded and the remaining components are added and kneaded may be used.

Further, in the production of the resin composition of the present invention, it is particularly preferred to use a twin-screw extruder, and both the co-rotating form and the counter-rotating form can be preferably used. L/D (the ratio of the effective length (L) of the screw of the extruder to the diameter (D) of the screw) is preferably 30 to 80, and the kneading disk can be used for the kneading segment. ), rotor, VCMT (trademark: Kobe Steel Works), spiral kneading (Twist Kneading, trademark: Nippon Steel Works), BMS (trademark: Nippon Steel Works) screw, etc. The kneading conditions are not particularly limited. For example, the kneading temperature is 150 ° C to 290 ° C, the shearing speed is 100 / s to 10000 / s, and the ratio of the motor power consumption per unit time of the kneading machine divided by the kneading amount per unit time is divided. The energy is 0.1 kW. H/kg~6 kW. H/kg. In addition, it is also possible to use a connection between a two-axis and a two-axis, a connection between a two-axis and a single-axis, and a connection between a continuous kneader and a two-axis. Further, the extruder manufacturers mentioned above include Nippon Steel Works, Kobe Steel Works, Werner, Ikebe, and Toshiba machines.

The resin composition thus obtained can be formed by injection molding, two-color injection molding, extrusion molding, rotational molding, press molding, hollow molding, sandow forming, compression molding, vacuum molding, or powder solidification molding (powder slush forming). A known method such as lamination molding, calender molding, or inflation molding is used for molding. Foaming, stretching, bonding, printing, coating, plating, etc. can also be performed as needed.

[formed body]

Since the resin composition of the present invention has the above-described configuration, it is excellent in balance of heat resistance, rigidity, impact resistance, surface impact resistance, tensile elongation at break, specularity, and interlayer peelability by using the resin composition. Shaped body.

Examples of the molded body include food packaging containers, various trays, sheets, tubes, films, fibers, laminates, electrical/electronic parts for coating or printing substrates, and office automation such as computers. (Office Automation, OA) equipment, housings for home appliances, interior and exterior parts, exterior parts, precision parts, construction materials, and other industrial parts. Moreover, in such a field of use, as described below, even if the resin composition of the present invention is foamed, it can be preferably used.

The resin composition of the present invention can also be foamed by using a foaming agent. The foaming method is not particularly limited, and may be any of a batch method or a continuous method. Specifically, it can be foamed by a molding method such as extrusion molding, injection molding, or press molding.

As the foaming agent, for example, a chemical foaming agent or a physical foaming agent can be used. The blowing agent can be selected according to the manufacturing method. The foaming agents may be used alone or in combination of two or more. Further, as the foaming agent, those described in Japanese Laid-Open Patent Publication No. 2012-229416 can be used.

<Chemical foaming agent>

Examples of the chemical foaming agent include a thermally decomposable foaming agent and a hollow particle foam.

Examples of the thermally decomposable foaming agent include a nitroso-based foaming agent such as N,N'-dinitrosopentamethylenetetramine; and an azo-based foaming agent such as azobiscarboxyguanamine; a sulfonium-based foaming agent such as p-oxy bisbenzenesulfonyl hydrazide; a triazine-based foaming agent such as trihydrazinotriazine; and 4-phenyltetrazole An azole-based foaming agent; an inorganic foaming agent such as sodium hydrogencarbonate. The thermally decomposable foaming agent may be used alone or in combination of two or more.

The amount of the thermally decomposable foaming agent to be added is not particularly limited, and is, for example, 0.1 parts by mass to 100 parts by mass based on 100 parts by mass of the resin composition excluding the thermally decomposable foaming agent.

The hollow particle type foaming agent refers to a heat-expandable microsphere which contains a swelling agent and has a thermoplastic resin as a shell component. Examples of the expansion agent constituting the hollow particle type foaming agent include the same foaming agents as the above-described thermal decomposition type foaming agent. Expansion agent The proportion of the hollow particle type foaming agent is preferably from 5% by mass to 30% by mass. The thermoplastic resin constituting the hollow particle type foaming agent may, for example, be a thermoplastic resin such as a homopolymer or a copolymer such as (meth)acrylonitrile. The thermoplastic resin may also be crosslinked or crosslinkable via a crosslinking agent such as divinylbenzene. The hollow particle type foaming agent may be used alone or in combination of two or more. The mass average particle diameter of the hollow particle type foaming agent (unexpanded microsphere state) is preferably from 1 μm to 100 μm.

The amount of the hollow particle-type foaming agent to be added is not particularly limited, and is, for example, 0.1 parts by mass to 100 parts by mass based on 100 parts by mass of the resin composition excluding the hollow particle type foaming agent.

<Physical foaming agent>

The resin composition of the present invention may be foamed by, for example, an aliphatic hydrocarbon such as propane; an alicyclic hydrocarbon such as cyclobutane; a halogenated hydrocarbon such as chlorodifluoromethane; an inorganic gas such as carbon dioxide, nitrogen or air; . Alternatively, a supercritical fluid (SF) may be used to form the foam. The supercritical fluid may, for example, be a supercritical fluid of nitrogen or carbon dioxide. In addition, in this specification, these are collectively called "physical foaming agent." The physical foaming agent may be used alone or in combination of two or more.

The amount of the physical foaming agent to be added is not particularly limited, and is, for example, 0.1 parts by mass to 100 parts by mass based on 100 parts by mass of the resin composition excluding the physical foaming agent.

In the foaming agent, the supercritical state is obtained at a relatively low temperature and pressure, the impregnation speed in the molten resin composition is fast, and the high concentration is additionally Supercritical carbon dioxide is preferred in terms of being suitable for foam molding and obtaining uniform bubbles.

<foaming nucleating agent>

The resin composition of the present invention may also contain a foaming nucleating agent (nucleating agent).

Examples of the foaming nucleating agent include powders of inorganic compounds such as calcium carbonate, talc, mica, cerium oxide, and titanium oxide. By including the foaming nucleating agent in the resin composition, the foaming unit diameter can be easily adjusted, and a foam molded article having appropriate flexibility or the like can be obtained.

The particle size of the foaming nucleating agent is preferably from 0.1 μm to 50 μm, more preferably from 0.1 μm to 20 μm. When the particle diameter of the foaming nucleating agent is at least the lower limit of the above range, the effect as a foaming nucleating agent is easily obtained, and the foaming unit diameter tends to be small, and the foaming unit diameter tends to be uniform. When the particle diameter of the foaming nucleating agent is at most the upper limit of the above range, the foaming unit diameter and the number of foaming units are appropriately changed, and the cushioning property of the foamed molded article tends to be excellent.

The content ratio of the foaming nucleating agent is preferably from 0 part by mass to 20 parts by mass, more preferably from 0.01 part by mass to 15 parts by mass, even more preferably from 0.1 part by mass to 10 parts by mass, per 100 parts by mass of the resin composition. Further, the foaming nucleating agent is preferably added to the molding machine in the form of, for example, a master batch of a polypropylene resin.

[Examples]

Hereinafter, an embodiment of the present invention will be described by way of examples, but the present invention is not limited by the examples. Furthermore, in the examples and comparative examples The parts and % are based on quality unless otherwise stated.

<Examples and Comparative Examples of Method for Producing Hydrogenated Conjugated Diene Block Copolymer>

<Manufacture of Hydrogenation Catalyst>

A hydrogenation catalyst (catalyst A and catalyst B) was produced by the following method.

Catalyst A

Catalyst A [bis(η5-cyclopentadienyl)titanium (tetrahydrofurfuryloxy) chloride] was obtained according to the description of Japanese Patent No. 3777810 (also known as "[chlorobis(2,4-ring) Pentadienyl) titanium (IV) tetrahydroindenyl alkoxide]"). Furthermore, the yield was 95%.

Catalyst B

Catalyst B [bis(η5-cyclopentadienyl)titanium (decyloxy) chloride] was obtained according to the description of Japanese Patent No. 3777810 (also known as "[chlorobis(2,4-cyclopentane)] Alkenyl) titanium (IV) decyl alkoxide]"). Furthermore, the yield was 97%.

<Physical property value of (hydrogenated) conjugated diene block copolymer)

The physical property values of the (hydrogenated) conjugated diene block copolymer were measured by the following methods. Among them, the physical property values of (5) to (8) are physical property values of the polymer finally obtained by subjecting the reaction liquid to solvent removal.

(1) Vinyl bond content (1, 2 bond content), etc.

The vinyl bond content (1, 2 bond content) was determined by infrared absorption spectroscopy (Morello method). Here, the unit of the vinyl bond content is a mol% basis. The content of the styrene unit was determined by preparing a calibration curve by an infrared absorption spectrometry (Morello method). Wherein, the unit of the content of the styrene unit is qualitative % basis.

(2) Weight average molecular weight (Mw)

The weight average molecular weight (Mw) is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8120).

. Developing solvent: tetrahydrofuran (TetraHydroFuran, THF)

. Measuring temperature: 40 ° C

. Column: TSKgel GMHx1

(3) Coupling rate

The coupling ratio is a value indicating to what extent all of the polymers contain a coupled or branched polymer. It was determined by GPC analysis based on the ratio of the coupled polymer after the addition of the coupling agent.

(4) Hydrogenation rate

The hydrogenation rate was calculated from a ¹ H-NMR spectrum at 400 MHz using carbon tetrachloride as a solvent.

(5) Melt flow rate (MFR)

The melt flow rate (MFR) was measured in accordance with JIS K7210 at a temperature of 230 ° C and a load of 2.16 kg. Further, the MFR after the heating promotion was measured by allowing the obtained polymer to stand in a thermostat adjusted to a temperature of 85 ° C and a humidity of 90% for one or three days.

(6) Change the quality (one / polymer one molecular chain)

Change the mass to the content of the N-containing polar group in the polymer, by Expressed in terms of the formula.

Change quality = polar group containing N atom / one polymer chain

The quality was determined by quantification of the amine titration method described in Analytical Chemistry (Analy. Chem.) 564 (1952). That is, after purifying the hydrogenated modified polymer, it is dissolved in an organic solvent, and methyl violet is used as an indicator, and HClO ₄ /CH ₃ COOH is titrated until the color of the solution changes from purple to water. Change the quality.

(7) 矽 alkyl protection rate (%)

The decyl group protection ratio is represented by the following formula.

矽alkyl protection ratio (%) = alkyl decyl group bonded to N atom in a polar group containing a N atom / alkyl decane bonded to N atom in a polar group containing a N atom a hydrogen atom on a N atom bonded to a polar group containing a N atom (a) × 100

Silicon group protection ratio is hydrogenated modified polymer after purification, deuterated chloroform as a solvent, at 400 MHz calculated from the ¹ H-NMR spectrum.

(8) decyl protecting group (single/polymer one molecular chain)

The decyl protecting group is represented by the following formula.

矽alkyl protecting group (number/polymer molecular chain) = alkyl decyl group bonded to N atom in a polar group containing N atom / (polymer molecular chain)

The decyl protecting group was obtained by purifying the hydrogenated modified polymer, using deuterated chloroform as a solvent, and calculating from ¹ H-NMR spectrum at 400 MHz. Further, the value of the molecular chain of the polymer was calculated from the value of the number average molecular weight (Mn) obtained by the gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8120).

[Example 1]

Adding 5000 g of cyclohexane, 150 g of tetrahydrofuran, 400 g of styrene, and 3-lithium-1-[N,N-double (three) as a polymerization initiator to a reaction vessel containing 10 L of internal volume substituted by nitrogen 2.88 g of methyl decyl)]aminopropane, and thermal polymerization was started from the polymerization initiation temperature of 50 °C. After completion of the reaction, the temperature was set to 20 ° C, 500 g of 1,3-butadiene was added, and thermal polymerization was carried out. After 30 minutes, 100 g of styrene was added, and further polymerization was carried out to obtain a reaction liquid containing a polymer.

Then, the reaction liquid was adjusted to 80 ° C or higher and hydrogen gas was introduced into the system.

Then, 0.32 g of the above-mentioned catalyst A and 0.39 g of tetrachloromethane were added, and the reaction was carried out for 1 hour while maintaining a hydrogen pressure of 1.0 MPa. After the reaction, the reaction solution was returned to normal temperature and normal pressure, and taken out from the reaction vessel to obtain a polymer solution.

Then, an aqueous solution (temperature: 80 ° C) whose pH is adjusted to 8.5 (pH at 80 ° C obtained by a glass electrode method, the same applies hereinafter) is added to the desolvation tank by ammonia as a pH adjuster, and further, The above polymer solution (the ratio of the above aqueous solution to 200 parts by mass with respect to 100 parts by mass of the polymer solution) was added, and steaming was carried out for 2 hours under the condition that the temperature of the liquid phase of the desolvation tank was 95 ° C (steam temperature) Desolvation was carried out at 190 ° C), and drying was carried out by a hot roll adjusted to a temperature of 110 ° C to obtain a hydrogenated modified polymer I-1.

[Comparative Example 1]

In Example 1, the aqueous solution was adjusted to pH 8.5 by ammonia. A hydrogenated modified polymer IA was obtained in the same manner as in Example 1 except that the pH was adjusted to 4.0 by an aqueous solution of sulfuric acid.

[Embodiment 2]

Using n-BuLi as a polymerization initiator, the amount of the polymerization initiator, the type and amount of the monomer, the polymerization temperature, and the polymerization time were obtained in such a manner as to become the polymer structure before hydrogenation shown in Example 2 of Table 1-1. The reaction liquid containing the polymer was obtained in accordance with Example 1 by the change. Then, 7.4 g of 4-[2-{N,N-bis(trimethyldecyl)amino}ethyl]styrene was added and reacted with the active site of the above polymer for 30 minutes.

Then, the reaction liquid was adjusted to 80 ° C or higher and hydrogen gas was introduced into the system.

Then, 2.97 g of dichlorotris(triphenylphosphine)ruthenium catalyst was added, and the reaction was carried out for 1 hour while maintaining a hydrogen pressure of 2.0 MPa. After the reaction, the reaction solution was returned to normal temperature and normal pressure, and taken out from the reaction vessel to obtain a polymer solution.

Then, dehydrogenation and drying were carried out in the same manner as in Example 1 except that an aqueous solution having a pH adjusted to 8.5 was used as the alkaline aqueous solution by using NaOH as a pH adjuster, thereby obtaining a hydrogenated modified polymer I- 2.

[Example 3]

Using n-BuLi as a polymerization initiator, the amount of the polymerization initiator, the kind and amount of the monomer, the polymerization temperature, and the polymerization time were obtained in such a manner as to become the polymer structure before hydrogenation shown in Example 3 of Table 1-1. The reaction liquid containing the polymer was obtained in accordance with Example 1 by the change. Then, 4.28 g of N,N-bis(trimethyldecyl)aminopropylmethyldimethoxydecane was added and reacted with the active point of the above polymer for 30 minutes.

Then, the reaction liquid was adjusted to 80 ° C or higher and hydrogen gas was introduced into the system. Then, 0.32 g of the above-mentioned catalyst A, 0.15 g of diethylaluminum chloride, and 0.27 g of n-BuLi were added, and the mixture was reacted for 1 hour while maintaining a hydrogen pressure of 1.0 MPa. After the reaction, the reaction solution was returned to normal temperature and normal pressure, and taken out from the reaction vessel to obtain a polymer solution.

Then, dehydrogenation and drying were carried out in the same manner as in Example 1 except that an aqueous solution having a pH adjusted to 8.5 was used as the alkaline aqueous solution by using NaOH as a pH adjuster, thereby obtaining a hydrogenated modified polymer I- 3.

[Example 4]

Using n-BuLi as a polymerization initiator, the amount of the polymerization initiator, the kind and amount of the monomer, the polymerization temperature, and the polymerization time were obtained in such a manner as to become the polymer structure before hydrogenation shown in Example 4 of Table 1-1. The reaction liquid containing the polymer was obtained in accordance with Example 1 by the change. Then, 4.23 g of N,N-bis(trimethyldecyl)aminopropylmethyldiethoxydecane was added and reacted with the active site of the above polymer for 30 minutes.

Then, the reaction liquid was adjusted to 80 ° C or higher and hydrogen gas was introduced into the system.

Then, 0.55 g of the above-mentioned catalyst A, 0.25 g of triethylaluminum, and 0.45 g of n-BuLi were added, and the reaction was carried out for 1 hour while maintaining a hydrogen pressure of 1.0 MPa. After the reaction, the reaction liquid was returned to 70 ° C at normal pressure and extracted from the reaction vessel to obtain a polymer solution.

Then, dehydrogenation and drying were carried out in the same manner as in Example 1 except that an aqueous solution having a pH adjusted to 8.5 was used as the alkaline aqueous solution by using NaOH as a pH adjuster, thereby obtaining a hydrogenated modified polymer I- 4.

[Example 5]

In Example 4, the pH was adjusted to 8.5 by NaOH. The hydrogenated modified polymer I-5 was obtained in the same manner as in Example 4 except that the solution was changed to an aqueous solution having a pH adjusted to 10.5 by NaOH.

[Embodiment 6]

In the same manner as in Example 4 except that the aqueous solution whose pH was adjusted to 8.5 was changed to an aqueous solution having a pH of 10.5 by ammonia with NaOH, the hydrogenated modified polymer I was obtained in the same manner as in Example 4. 6.

[Comparative Example 2]

In the same manner as in Example 4 except that the aqueous solution whose pH was adjusted to 8.5 was changed to an aqueous solution having a pH of 4.0 by sulfuric acid, the hydrogenated modified polymer I-B was obtained in the same manner as in Example 4.

[Comparative Example 3]

In the same manner as in Example 4 except that the pH was adjusted to 8.5 by NaOH, the hydrogenated modified polymer I-C was obtained in the same manner as in Example 4.

[Embodiment 7]

The amount of the polymerization initiator, the type and amount of the monomer, the polymerization temperature, the polymerization time, the hydrogenation catalyst, and the like were changed so as to be the polymer structure before hydrogenation shown in Example 7 of Table 1-2, according to Examples 4 A reaction liquid containing a polymer and a hydrogenated modified polymer I-7 were obtained.

[Embodiment 8]

3-litho-1-[N,N-bis(trimethyldecyl)aminopropane was used as a polymerization initiator, and the polymer structure before hydrogenation shown in Example 8 of Table 1-2 was used. The amount of the polymerization initiator, the type and amount of the monomer, the polymerization temperature, the polymerization time, and the like were changed, and a reaction liquid containing a polymer was obtained in accordance with Example 1. Then, 4.23 g of N,N-bis(trimethyldecyl)aminopropylmethyldiethoxydecane was added and reacted with the active site of the above polymer for 30 minutes. Then, the reaction liquid was adjusted to 80 ° C or higher, and hydrogen gas was introduced into the system, and a hydrogenation reaction, solvent removal, and drying were carried out in the same manner as in Example 3 to obtain a hydrogenated modified polymer I-8.

[Embodiment 9]

Adding 5000 g of cyclohexane, 3.6 g of propylene glycol ethyl propyl ether, 50 g of 1,3-butadiene, and 1,3-stretching as a polymerization initiator to a reaction vessel with a volume of 10 L substituted with nitrogen 5.1 g of phenyl-bis-(3-methyl-1-phenylpentylene)dilithium was subjected to thermal polymerization at a polymerization initiation temperature of 20 ° C for 30 minutes. Further, 750 g of 1,3-butadiene was added, and thermal polymerization was carried out for 30 minutes. Further, 200 g of styrene was added and polymerization was carried out to obtain a reaction liquid containing a polymer. Then, 8.23 g of N,N-bis(trimethyldecyl)aminopropylmethyldiethoxydecane was added and reacted with the active site of the above polymer for 30 minutes.

Then, the reaction liquid was adjusted to 80 ° C or higher and hydrogen gas was introduced into the system.

Then, 0.78 g of the above catalyst A, 0.66 g of diethylaluminum chloride and 0.65 g of n-BuLi were added, and the mixture was reacted for 1 hour while maintaining a hydrogen pressure of 1.0 MPa. After the reaction, the reaction solution was returned to normal temperature and normal pressure, and taken out from the reaction vessel to obtain a polymer solution. Then, desolvation and drying were carried out in the same manner as in Example 1 to obtain a hydrogenated modified polymer I-9.

[Embodiment 10]

Using n-BuLi as a polymerization initiator, the amount of the polymerization initiator, the type and amount of the monomer, the polymerization temperature, and the polymerization time were obtained in such a manner as to become the polymer structure before hydrogenation shown in Example 10 of Table 1-2. The reaction liquid containing the polymer was obtained in accordance with Example 1 by the change. Then, 6.9 g of N,N-bis(trimethyldecyl)aminopropylmethyldiethoxydecane was added and reacted with the active site of the above polymer for 30 minutes.

Then, the reaction liquid was adjusted to 80 ° C or higher and hydrogen gas was introduced into the system.

Then, 0.19 g of the above-mentioned catalyst A and 1.25 g of diethylaluminum chloride were added, and the reaction was carried out for 1 hour while maintaining a hydrogen pressure of 1.0 MPa. After the reaction, the reaction solution was returned to normal temperature and normal pressure, and taken out from the reaction vessel to obtain a polymer solution.

Then, the aqueous solution was subjected to solvent removal and drying in the same manner as in Example 1 except that an aqueous solution having a pH adjusted to 8.5 was used as the alkaline aqueous solution by using NaOH as a pH adjuster, thereby obtaining a hydrogenated modified polymer I-10. .

[Example 11]

Using n-BuLi as a polymerization initiator, the amount of the polymerization initiator, the type and amount of the monomer, the polymerization temperature, and the polymerization time were obtained in such a manner as to become the polymer structure before hydrogenation shown in Example 11 of Table 1-2. The reaction liquid containing the polymer was obtained in accordance with Example 1 by the change. Then, 1.8 g of N,N-bis(trimethyldecyl)aminopropylmethyldiethoxydecane was added and reacted with the active site of the above polymer for 30 minutes.

Then, the reaction liquid was adjusted to 80 ° C or higher and hydrogen gas was introduced into the system.

Then, 0.58 g of the above catalyst A and 0.65 g of diethylaluminum chloride were added, and the mixture was reacted for 1 hour while maintaining a hydrogen pressure of 1.0 MPa. After the reaction, the reaction solution was returned to normal temperature and normal pressure, and taken out from the reaction vessel to obtain a polymer solution.

Then, dehydrogenation and drying were carried out in the same manner as in Example 1 except that an aqueous solution having a pH adjusted to 8.5 was used as the alkaline aqueous solution by using LiOH as a pH adjuster, thereby obtaining a hydrogenated modified polymer I- 11.

[Embodiment 12]

4,500 g of cyclohexane, 2.36 g of 2,2-bis(tetrahydrofuranyl)propane, 150 g of styrene, and n-BuLi 1.2 g as a polymerization initiator were added to a reaction vessel with a volume of 10 L substituted with nitrogen. The heat-insulating polymerization was started from the polymerization starting temperature of 50 °C. After completion of the reaction, the temperature was set to 20 ° C, 730 g of 1,3-butadiene was added, and thermal polymerization was carried out. After 30 minutes, 100 g of styrene was added, and further polymerization was carried out. After the completion of the reaction, 20 g of 1,3-butadiene was added, and further polymerization was carried out to obtain a reaction liquid containing a polymer. Then, 4.6 g of N,N-bis(trimethyldecyl)aminopropylmethyldiethoxydecane was added and reacted with the active point of the above polymer for 30 minutes.

Then, the reaction liquid was adjusted to 80 ° C or higher and hydrogen gas was introduced into the system.

Then, 0.32 g of the above-mentioned catalyst A and 0.32 g of n-BuLi were added, and the reaction was carried out for 1 hour while maintaining a hydrogen pressure of 1.0 MPa. After the reaction, the reaction solution was returned to normal temperature and normal pressure, and taken out from the reaction vessel to obtain a polymer solution.

Then, dehydrogenation and drying were carried out in the same manner as in Example 1 except that an aqueous solution having a pH adjusted to 8.5 was used as the alkaline aqueous solution by using NaOH as a pH adjuster, thereby obtaining a hydrogenated modified polymer I- 12.

[Example 13] Production of hydrogenated modified SEBC polymer [(styrene block) - (medium 1, 2 bond content butadiene block) - (low 1, 2 bond content butadiene block)]

Add cyclohexane to a 10 L reaction vessel filled with nitrogen 5000 g, 0.25 g of tetrahydrofuran, 300 g of 1,3-butadiene, and n-BuLi 0.9 g as a polymerization initiator were subjected to heat-insulation polymerization from a polymerization initiation temperature of 70 °C. After completion of the reaction, the temperature was set to 30 ° C, and 18 g of tetrahydrofuran and 500 g of 1,3-butadiene were added and heat-insulated. After 30 minutes, 200 g of styrene was added and reacted for 30 minutes. The first polymer of the obtained polymer had a 1,2 bond content of 14 mol%, and the second stage butadiene block had a 1,2 bond content of 50 mol%.

Then, 4.13 g of N,N-bis(trimethyldecyl)aminopropylmethyldiethoxydecane was added and reacted with the active point of the above polymer for 30 minutes. Then, a hydrogenation reaction, solvent removal, and drying were carried out in the same manner as in Example 3 to obtain a hydrogenated modified polymer I-13.

[Comparative Example 4]

In the same manner as in Example 13, except that an aqueous solution having a pH adjusted to 8.5 was changed to an aqueous solution having a pH of 4.0 by sulfuric acid, the hydrogenated modified polymer I-D was obtained in the same manner as in Example 13.

[Example 14] Hydrogenated modified CEBC polymer [(low 1, 2 bond content butadiene block) - (high 1, 2 bond content butadiene block) - (low 1, 2 bond content butadiene Manufacture of block)]

Adding 5000 g of cyclohexane, 0.25 g of tetrahydrofuran, 300 g of 1,3-butadiene, and n-BuLi 0.85 g as a polymerization initiator to the reaction vessel with a volume of 10 L substituted by nitrogen, starting from the polymerization The thermal polymerization was started at a temperature of 70 °C. After completion of the reaction, the temperature was set to 20 ° C, and 75 g of tetrahydrofuran and 700 g of 1,3-butadiene were added and heat-insulated. Then, N,N-bis(trimethyldecyl) is added to the system. 0.4 g of aminopropyltrimethoxydecane, and further 2.0 g of methyldichlorodecane, was reacted for 30 minutes. The first-stage butadiene block of the obtained polymer had a 1,2 bond content of 14%, and the second-stage butadiene block had a 1,2 bond content of 80%. Then, a hydrogenation reaction, solvent removal, and drying were carried out in the same manner as in Example 4 to obtain a hydrogenated modified polymer I-14.

[Comparative Example 5]

In the same manner as in Example 14, except that an aqueous solution having a pH of 8.5 was adjusted to a pH of 4.0 by sulfuric acid, the hydrogenated modified polymer I-E was obtained.

[Example 15] Hydrogenated modified CEBC polymer [(low 1, 2 bond content butadiene block) - (medium 1, 2 bond content butadiene block) - (low 1, 2 bond content butadiene) Manufacture of block)]

Adding 5000 g of cyclohexane, 0.25 g of tetrahydrofuran, 300 g of 1,3-butadiene, and n-BuLi 0.85 g as a polymerization initiator to the reaction vessel with a volume of 10 L substituted by nitrogen, starting from the polymerization The thermal polymerization was started at a temperature of 70 °C. After completion of the reaction, the temperature was set to 20 ° C, and 5.0 g of tetrahydrofuran and 700 g of 1,3-butadiene were added to carry out thermal polymerization. Then, 0.4 g of N,N-bis(trimethyldecyl)aminopropyltrimethoxydecane was added to the system, and 2.3 g of methyldichloromethane was further added thereto, followed by a reaction for 30 minutes. The first-stage butadiene block of the obtained polymer had a 1,2 bond content of 14%, and the second-stage butadiene block had a 1,2 bond content of 34%. Then, a hydrogenation reaction, solvent removal, and drying were carried out in the same manner as in Example 4 to obtain a hydrogenated modified polymer I-15.

[Example 16]

In Example 4, as a solvent removal and drying step, by means of an evaporator (Evaporator) The hydrogenation modification was carried out in the same manner as in Example 4 except that the polymer solution was concentrated to a TSC of 50%, and then desolvation and drying were carried out using a vacuum dryer set at 60 ° C and 0.001 MPa. Polymer I-16.

[Example 17]

In the same manner as in Example 4, the hydrogenation-modified polymerization was carried out in the same manner as in Example 4 except that the polymer solution was directly desolvated and dried on a hot roll adjusted to a temperature of 110 ° C as a solvent removal and drying step. Item I-17.

[Comparative Example 6 to Comparative Example 10]

As a comparative example, the unmodified hydrogenated polymer I-F to unmodified hydrogenated polymer I-J shown in Table 3 was produced.

The above results are shown in the following table.

In Comparative Example 6 to Comparative Example 10, since the unmodified hydrogenated polymer IF to the unmodified hydrogenated polymer IJ was used, the MFR retention rate was high, but the resin composition containing the polymer and other polymers was used. In the case of producing a molded body (refer to the comparative example described later), the physical properties of the obtained molded body are not satisfactory.

<Example and Comparative Example of Resin Composition>

<Evaluation method of test piece>

(1) Rigidity

The flexural modulus of the test piece was measured according to ISO 178 by a Three-point Bending Test at a temperature of 23 °C. The magnitude of the bending elastic modulus was used as an index indicating the rigidity of the test piece.

(2) Impact resistance (Charpy impact strength)

The Charpy impact strength of the test piece was measured by a Charpy impact tester at a temperature of 23 ° C according to ISO 179. The magnitude of the Charpy impact strength was used as an index indicating the impact resistance of the test piece.

(3) Impact resistance (surface impact)

As another index indicating the impact resistance of the test piece, the surface impact resistance of the test piece was measured. The surface impact property is a flat test piece having a length of 80 mm, a width of 55 mm, and a thickness of 2.4 mm obtained by injection molding of the resin composition obtained in the examples and the like, and placed on a hole of 25 mm φ, using a hemisphere at the front end. The 15.7 mm φ striking bar hit the test piece at a speed of 2.4 mm/sec, and the breaking energy was calculated from the displacement until the test piece was broken and the load was measured. The amount of energy destroyed is used as an indicator of surface impact.

(4) tensile breaking strength, tensile elongation at break, tensile strength and strain

The tensile test of the test piece was carried out in accordance with ISO 527 at a temperature of 23 ° C, and tensile fracture strength, tensile elongation at break, and tensile strength drop strain were measured.

(5) Mirror surface

The surface of the test piece in which the resin composition obtained in the Example and the like was formed into a flat shape by injection molding was visually observed in accordance with the following criteria, and the specularity of the test piece was evaluated.

○: The distortion of the image reflected in the test piece was small.

△: The deformation of the image reflected in the test piece was between ○ and ×.

×: The image reflected in the test piece has a large deformation.

(6) Interlayer peeling

In the test piece in which the resin composition obtained in the example and the like was formed into a flat shape by injection molding, a notch was cut out in a checkerboard shape by a cutter, and an adhesive tape was attached to the notch (adhesive tape). Then, the release tape was gradually pulled by the angle formed by the tape and the test piece at 90 degrees, and it was visually confirmed whether at least a part of the surface layer of the test piece was peeled off, and the interlayer peeling of the test piece was evaluated according to the following criteria.

○: The surface was not peeled off.

×: The surface was peeled off.

(7) Stress residual rate

The stress residual ratio is obtained by a stress relaxation test (bending stress). By the three-point bending test method (clamp width: 81.6 cm), the thickness of the resin composition was formed by injection molding at a temperature of 23 ° C at a speed of 20 mm/min × length × width = 2 mm × 40 mm × The 100 mm flat test piece was bent until the deformation reached 18% and was maintained. Thereafter, the time at which the constant strain (deformation 18%) was given and the start of holding (0 second) was set as the initial stress, and the stress after 500 seconds was measured. Variety. The stress relaxation rate was calculated as the initial stress (0 sec)/stress change (500 sec).

(8) Chemical resistance

Chemical resistance (solvent stress cracking) is obtained by a bent strip method. A test piece having a thickness of × length × width = 2 mm × 40 mm × 50 mm was cut out from the test piece obtained by injection molding of the resin composition, and a non-penetrating slit was cut out from the surface, and bent and embedded into a dedicated one. In the jig, dilute the "bubble force" (trade name: manufactured by Lion Co., Ltd.) adjusted to 50 ° C with water, and place it in a solution adjusted to 22% nonionic solution to 10 Five of the test pieces were evaluated for the time of cracking (50% rupture time).

[Example 1A]

Hydrogenated modified polymer I-2 obtained in Example 2 as component (I) and polyethylene terephthalate as component (II) (trade name "RT523C" Japanese Unicorn (Unipet Japan) (manufactured by the company), the moisture ratio is reduced to 200 ppm or less by a vacuum dryer (manufactured by Satake Chemical Industry Co., Ltd.), and the mixing ratio (mass basis) (I) / (II) = 10% / 90%, and The strands were heated and kneaded at 270 ° C using a 40 mm φ twin-screw extruder (manufactured by Chiba Corporation), and then the strands were cut by a pelletizer, thereby obtaining granules. Resin composition. The obtained pellets were dried at 80 ° C for 5 hours by a dehumidifying dryer (manufactured by Satake Chemical Industry Co., Ltd.), and then molded at a processing temperature of 270 ° C by an injection molding machine (manufactured by Nippon Steel Works Co., Ltd.) to obtain physical property evaluation. Test piece.

Further, in order to measure the physical properties after the heating promotion of the component (I), the component (I) obtained in the examples was allowed to stand in a thermostat adjusted to a temperature of 85 ° C and a humidity of 90% for 3 days, and then the components after the placement were used. (I) A test piece was obtained in the same manner as above.

[Example 2A to Example 4A, Example 1B, Example 1C to Example 4C, Example 1D to Example 6D, Example 1E, Example 1F to Example 7F, Example 1G to Example 2G, Implementation Example 1H, Example 1I, Example 1J, Example 1K to Example 7K; Comparative Example 1A to Comparative Example 3A, Comparative Example 1B to Comparative Example 3B, Comparative Example 1C to Comparative Example 3C, Comparative Example 1D to Comparative Example 3D Comparative Example 1E to Comparative Example 3E, Comparative Example 1F to Comparative Example 6F, Comparative Example 1G to Comparative Example 3G, Comparative Example 1H to Comparative Example 3H, Comparative Example 1I to Comparative Example 3I, Comparative Example 1J to Comparative Example 3J, and Comparison Example 1K~Comparative Example 4K]

In the same manner as in Example 1A, the resin composition and the test piece were obtained in the same manner as in Example 1A except that the type, the mixing ratio, and the processing temperature of the compounding components were changed as described in Tables 1 to 14.

Various measurements were carried out using the test pieces obtained above. The results are shown in Tables 4 to 14.

For example, when Example 3A and Comparative Example 1A to Comparative Example 3A are compared in Table 4, the following can be seen. (1) The molded article containing only PET has poor impact resistance and tensile elongation at break. (2) The molded article including the unmodified hydrogenated polymer and PET has poor physical properties such as impact resistance, tensile elongation at break, specularity, and interlayer peeling. (3) A polymer having a low alkylene group-protecting ratio obtained by performing solvent removal under conditions other than the present invention, which is a hydrogenated modified polymer, has poor stability over time, and therefore contains heat. The formed polymer and the molded body of PET have various physical properties. With respect to these, (4) is a hydrogenated modified polymer, and a polymer having a high alkylene group-protecting ratio obtained by performing solvent removal under the conditions of the present invention has excellent stability with time, and therefore includes the heat-promoted polymer. The polymer and the molded body of PET have excellent balance of various physical properties.

Further, when Example 1K to Example 7K and Comparative Example 1K to Comparative Example 4K were compared in Table 14, the following would be known. (1) The molded body including only PLA has a low drop strain, a high residual stress rate, and poor stress crack resistance. (2) The molded body containing only PE has a high drop strain and a low residual stress rate, but is inferior in stress crack resistance. (3) The molded body including PLA and PE has low drop strain, high residual stress rate, and poor stress crack resistance. The comparative example has poor stress crack resistance. With respect to these, (4) a molded article comprising a hydrogenated modified polymer (and optionally a modified polyolefin) and PLA (PET) or PE has a high drop strain, a low residual stress rate, and a stress crack resistance. Also excellent. That is, by adding the hydrogenated modified polymer of the present invention to the alloy material of PLA (PET) and PE, the strain at break can be increased, the stress residual ratio can be lowered, and the stress crack resistance can be greatly improved. The stress crack resistance is related to the strain and the residual stress rate (stress relaxation). The higher the strain at break and the lower the residual stress rate, the better the stress crack resistance. Further, the stress crack resistance can be improved by optimizing the amount of the hydrogenated modified polymer or by using it in combination with the modified polyolefin. Further, a method of modifying a rubber in which an ethylene-based elastomer, LDPE, or LLDPE is added as a stress cracking improvement can be used.

Further, the resin materials used in the examples and comparative examples were as follows.

. Ingredient (I): Hydrogenated modified polymer obtained in the above examples

. PET: Polyethylene terephthalate (trade name "RT523C", manufactured by Unipet, Japan)

. PLA: Polylactic acid (trade name "Ingeo 3001D", manufactured by NatureWorks)

. PE1: Polyethylene (trade name "Novatec UF331", manufactured by Polypro, Japan)

. PE2: Polyethylene (trade name "Novatec UJ960", manufactured by Polypro, Japan)

. PE3: High-density polyethylene (trade name "HJ340", manufactured by Polychem Corporation, Japan)

. PE4: High-density polyethylene (trade name "HJ560", manufactured by Japan Polyethylene Corporation)

. PP1: Polypropylene (trade name "BC03C", manufactured by Polypro, Japan)

. PP2: Polypropylene (trade name "PMB60A", manufactured by Prime Polymer)

. PP3: Polypropylene (trade name "MA04", manufactured by Polypro, Japan)

. PMMA: Polymethyl methacrylate (trade name "Parapet G", manufactured by Kuraray)

. EVOH: ethylene-vinyl alcohol copolymer (trade name "EP-F101", manufactured by Kuraray Co., Ltd.)

. PA: Polyamide (trade name "T802", manufactured by Toyobo Co., Ltd.)

. BF-E: EGMA (trade name "Bondfast-E", manufactured by Sumitomo Chemical Co., Ltd.)

. EO: ethylene-based copolymer (trade name "Engage 8150", manufactured by Dow Chemical Co., Ltd.)

Claims (9)

A resin composition comprising: a hydrogenated conjugated diene block copolymer having a group selected from the group consisting of the formula (i), a group represented by the formula (ii), and a formula represented by the formula (iii) At least one group in the group, and the sulfonyl group protection ratio of the N atom in the N atom-containing polar group determined by the following is 70% or more; and is selected from the group consisting of a nonpolar polymer, a polar polymer, and a filler At least one of them; In the formulae (i) to (iii), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Or an organic decyloxy group having 1 to 100 carbon atoms; R ⁴ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms; and R ⁵ represents a carbon number of 1 ~12 divalent hydrocarbon group]; decyl group protection ratio (%) = (Si atom bonded to N atom in a polar group containing N atom) / [(bonded to a polar group containing a N atom) Si atom(s) on the N atom in the middle) + (hydrogen atom bonded to the N atom in the polar group containing the N atom)] × 100 (the above formula indicating the alkylidene protection ratio (%) In the above, the N-containing polar group refers to a group represented by the formula (i) to the formula (iii), and at least one of the groups represented by the above formulas (i) to (iii). -SiR ¹ R ² R ³ or -SiR ¹ R ² -R ⁵ -SiR ¹ R ² - a group derived from a group represented by a group). A method for producing a hydrogenated conjugated diene block copolymer, comprising the steps of: (1) having a group selected from the group represented by the formula (i), a group represented by the formula (ii), and a formula (iii) a step of hydrogenating a conjugated diene block copolymer of at least one of the groups represented by the group; and (2) copolymerization of the hydrogenated conjugated diene block obtained from the above step (1) In the reaction liquid of the substance and the solvent, the solvent is removed by at least one selected from the following (a) to (c): (a) removing the solvent by bringing the reaction liquid and the alkaline aqueous solution into contact with steam. a method, (b) the method of continuously or intermittently supplying the reaction liquid to a vessel maintained at 50 ° C to 260 ° C and 0.01 kPa to 0.1 MPa, and (c) supplying the reaction liquid to a heating a method of rotating a roller of a temperature of 80 ° C to 260 ° C; In the formulae (i) to (iii), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Or an organic decyloxy group having 1 to 100 carbon atoms; R ⁴ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms; and R ⁵ represents a carbon number of 1 ~12 divalent hydrocarbon group]. The method for producing a hydrogenated conjugated diene block copolymer according to the second aspect of the invention, wherein, in the case where the step (2) of removing the solvent is the method (a), the temperature of the alkaline aqueous solution is 50 ° C ~ 150 ° C. The method for producing a hydrogenated conjugated diene block copolymer according to the second aspect of the invention, wherein, in the case where the step (2) of removing the solvent is the method (a), the pH of the alkaline aqueous solution It is 8 or more. The method for producing a hydrogenated conjugated diene block copolymer according to any one of claims 2 to 4, wherein the conjugated diene block copolymer has a selected from the group consisting of A block copolymer of two or more polymer blocks in the polymer block of A) to (D): (A) an aromatic alkenyl polymer having an aromatic alkenyl compound unit amount of 80% by mass or more a block; (B) a conjugated diene compound unit in an amount of 80% by mass or more, and a 1,2 bond content and a 3,4 bond content in total of less than 30 mol% of a conjugated diene polymer block; a conjugated diene polymer block having a conjugated diene compound unit content of 80% by mass or more and a 1,2 bond content and a 3,4 bond content of 30 mol% to 90 mol% in total; (D) a conjugated diene The amount of the compound unit exceeds 20% by mass and is less than 80% by mass A random copolymer block of a conjugated diene compound and an aromatic alkenyl compound. The method for producing a hydrogenated conjugated diene block copolymer according to any one of claims 2 to 4, wherein the conjugated diene block copolymer is selected from the group consisting of The polymer obtained by at least one of the methods [A] to [E]: [A] at least the organic compound of the conjugated diene compound having at least one group represented by the above formula (i) to formula (iii) a method of obtaining a conjugated diene block copolymer by reacting in the presence of an alkali metal compound; [B] at least a conjugated diene compound and at least one group represented by the above formula (i) to formula (iii) a method of reacting an unsaturated monomer to obtain a conjugated diene block copolymer; [C] bringing a polymerization stopper having at least one group represented by the above formula (i) to formula (iii) at least a method of reacting an active point of a block copolymer obtained by polymerization of a conjugated diene compound to obtain a conjugated diene block copolymer; [D] having at least one of the above formulas (i) to (iii) The coupling agent of the group reacts with the active point of at least the block copolymer obtained by polymerizing the conjugated diene compound to obtain a total of the conjugated diene block. Method of the compound; [E] activity of a block copolymer obtained by polymerizing an unsaturated monomer having at least one group represented by the above formula (i) to formula (iii) with at least a conjugated diene compound A reaction is carried out to obtain a conjugated diene block copolymer. A hydrogenated conjugated diene block copolymer obtained by the method for producing a hydrogenated conjugated diene block copolymer according to any one of claims 2 to 4. A resin composition comprising: the hydrogenated conjugated diene block copolymer as described in claim 7; and at least one selected from the group consisting of a nonpolar polymer, a polar polymer, and a filler. A molded body obtained by molding a resin composition as described in claim 1 or 8.