JPH11240998A - Block copolymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a block copolymer composition having a high degree of swelling for an ester compound and excellent in liquid holding properties and, on the other hand, excellent in mechanical strength or shape retaining properties. SOLUTION: This block copolymer composition contains a block copolymer comprising a segment A containing 10-100 mol.% of a polar monomer selected from a polar monomer 1 having (1) a polymerizable unsaturated bond and a functional group selected from hydroxy group, nitrile group, carboxyl group, amino group and amide group, a polar monomer 2 represented by the formula CH2 =CR<1> -COO-(CH2 -CHR<2> -O)t -R<3> [R<1> and R<2> are each hydrogen atom or a 1-5C alkyl group; R<3> is a 1-5C alkyl group or phenyl group; (t) is a number of repetition and an integer of 1-25] and a polar monomer 3 represented by the formula CH2 =CR<4> -COO-(Cm H2m -COO)n -R<5> [R<4> is a 1-5C alkyl group; R<5> is a 1-10C alkyl group or phenyl group; (n) and (m) are each a number of repetition and an integer of 1-20] as constituent components and a segment B containing <10 mol.% of the polar monomer as a constituent component and (2) an ester compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a block copolymer composition. More specifically, the block copolymer composition has excellent affinity between a block copolymer as a constituent component and an ester compound, but also has excellent mechanical strength. The present invention relates to a block copolymer composition most suitable for applications such as a hydrophilic resin.

[0002]

2. Description of the Related Art In order to obtain devices such as electrochromic display elements, recording elements, batteries and sensors, an organic solvent (electrolyte solution) in which a metal salt is dissolved in a polymer.
, And a solid electrolyte prepared by swelling is used. As such a solid electrolyte, specifically, a polar polymer (polyacrylonitrile) impregnated with a metal salt electrolyte (M. Watanabe et al., J. Polymer Sci.
Polym. Phis., 21, 939 (1983)), photocuring by irradiating a fixed amount of ultraviolet light to a liquid mixture consisting of a polar polymer, an electrolyte solution (an organic solvent in which a metal salt is dissolved), and a photosensitive crosslinking agent. (K. Abraham and M. Alamgir, J. Ele
ctrochem. Soc., 137, 1657 (1990)).

On the other hand, photocurable resins are frequently used as printing substrates. As such a photocurable resin, specifically, an acrylic monomer or oligomer such as methyl methacrylate or an epoxy monomer such as bisphenonol A is used as a main component, and for a low molecular weight material of the main component, The photopolymerization initiator and the photosensitizer are added in predetermined amounts, respectively.

[0004]

However, the conventional solid electrolyte has a problem in that the polar polymer itself is plasticized by the electrolyte solution, and the mechanical strength of the polar polymer tends to be greatly reduced. Therefore, it was difficult for the conventional solid electrolyte to maintain a constant shape for a long period of time (form retention). Further, in the conventional solid electrolyte, the affinity between the polar polymer and the electrolyte solution is insufficient, so that there has been a problem that the electrolyte solution is likely to ooze out when stored (stored) for a long time. Furthermore, since a polar polymer such as polyacrylonitrile has a high melting point and cannot be processed unless the temperature is high, there is a problem that it is difficult to manufacture a lithium secondary battery or the like using the polar polymer.

On the other hand, the conventional photocurable resin has a problem that it is not easy to handle because a low molecular weight monomer or oligomer is used as a main component. Therefore, it has been proposed to improve the handleability by adding a rubber component or a resin component as a high molecular weight component to these monomers or oligomers. However, since acrylic monomers and epoxy monomers have high polarity, there are problems such as the types of high molecular weight components to be added are extremely limited, or compatibility with the high molecular weight components to be added is not sufficient.

[0006] The present invention has been made in view of the above-mentioned problems, and has excellent mechanical strength by using a specific block copolymer as a constituent component.
It is an object of the present invention to provide a block copolymer composition in which the shape does not change with time even after swelling. Another object of the present invention is to provide a block copolymer composition which has an improved affinity with an ester compound and has a low risk of leaching of the ester compound even when stored (stored) for a long period of time.

Another object of the present invention is to provide a block copolymer composition which can be easily produced.

[0008]

According to the present invention, there is provided a block copolymer composition having the following features. That is, (1) at least one polar monomer selected from the group consisting of the following polar monomer 1, the following polar monomer 2 and the following polar monomer 3 is contained as a constituent component in an amount of 10 to 100 mol%. A block copolymer consisting of segment A and segment B containing less than 10 mol% of the polar monomer as a constituent;
(2) It contains at least an ester compound.

Polar monomer 1: has at least one polymerizable unsaturated bond and at least one functional group selected from the group consisting of a hydroxy group, a nitrile group, a carboxyl group, an amino group and an amide group. It is a polar monomer.

Polar monomer 2: A polar monomer represented by the following general formula (1).

[0011] ^{_{CH 2 = CR 1 -COO- (CH}} 2 -CHR 2 -O) t -R 3 ·· (I)

[In the general formula (I), R ¹ and R ²
Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ³ is an alkyl group having 1 to 5 carbon atoms or a phenyl group;
Is the number of repetitions and is an integer of 1 to 25. ]

Polar monomer 3: A polar monomer represented by the following general formula (2).

CH ₂ ＣＲCR ⁴ —COO— (C _m H _2m —COO) _n —R ⁵ (2)

[In the general formula (2), R ⁴ has 1 carbon atom.
R ⁵ is an alkyl group having 1 to 10 carbon atoms or a phenyl group, n and m are the number of repetitions,
Each is an integer of 1 to 20. ]

In constituting the block copolymer composition of the present invention, it is preferable that the segment B contains a styrene compound as a main component. When the styrene compound is contained as described above, the mechanical strength of the block copolymer composition can be further improved.

In constructing the block copolymer composition of the present invention, the weight ratio of segment A to segment B (segment A / segment B) is set to 20 to 9
It is preferable to set the value in the range of 0% by weight / 10 to 80% by weight. With this configuration, the mechanical strength of the block copolymer composition and the affinity for the ester compound and the like can be exhibited in a well-balanced manner.

In constituting the block copolymer composition of the present invention, the average molecular weight (Mn) of the block copolymer in terms of polystyrene is from 5,000 to 5,000.
It is preferable to set the value in the range of 000. With such a configuration, the mechanical strength of the block copolymer composition and the affinity for the ester compound and the like can be exhibited in a well-balanced manner, and the production and handling of the block copolymer composition are further facilitated.

Further, in constituting the block copolymer composition of the present invention, the content of the ester compound is 10 to 1,000 per 100 parts by weight of the block copolymer.
The value is preferably within a range of 0 parts by weight. With this configuration, the mechanical strength of the block copolymer composition and the affinity for the ester compound and the like can be exhibited in a better balance.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the block copolymer composition of the present invention will be specifically described. First, the first embodiment of the present invention comprises (1) a polar monomer 1,
Segment A containing a specific amount of at least one polar monomer selected from the group consisting of polar monomer 2 and polar monomer 3 as a component and a segment containing a specific amount of the polar monomer as a component A block copolymer composed of B (sometimes referred to as a first component); and (2)
It is a block copolymer composition containing an ester compound (may be referred to as a second component).

1. Block Copolymer The block copolymer, which is the first component in the block copolymer composition of the present invention, includes the segment A and the segment B as described above.

(1) Segment A The segment A is included to improve the affinity with the ester compound. Therefore, at least one polar monomer among the polar monomers 1 to 3 shown below is included as a component. Further, the amount of the polar monomer is limited within a range of 10 to 100 mol%. That is, by containing a specific polar monomer in a specific amount as described above, the affinity between the block copolymer and the ester compound can be significantly improved.

Polar monomer 1: has at least one polymerizable unsaturated bond and at least one functional group selected from the group consisting of a hydroxy group, a nitrile group, a carboxyl group, an amino group and an amide group. It is a polar monomer.

Specifically, preferred examples of the polar monomer having a hydroxy group in the polar monomer 1 include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and ethylene glycol mono (meth) acrylate. Acrylates, mono (meth) acrylates of polyalkylene glycol (alkylene glycol having 2 to 12 repeating units), and 1 such as hydroxystyrene
Species or two or more species. In addition, these polar monomers can be arbitrarily selected according to the purpose of use.

Preferred examples of the polar monomer having a nitrile group in the polar monomer 1 include acrylonitrile, methacrylonitrile, α-ethylacrylonitrile, methyl α-isopropylacrylonitrile, methyl α-n-butylacrylonitrile, -Cyanoethyl (meth) acrylate or 2- (2-cyanoethoxy)
One or more of ethyl alcohol, 3- (2-cyanoethoxy) propyl alcohol, (meth) acrylate of 4- (2-cyanoethoxy) butyl alcohol and 2- [2- (2-cyanoethoxy) ethoxy] ethyl alcohol; Two or more types are mentioned. In addition, these polar monomers can be arbitrarily selected according to the purpose of use.

Preferred examples of the carboxyl group-containing polar monomer in the polar monomer 1 include acrylic acid,
One or more half esters of a dicarboxylic acid such as methacrylic acid, maleic acid, fumaric acid, itaconic acid, tetraconic acid, succinic acid, or fumaric acid and an unsaturated alcohol having a polymerizable group (reactive group). Is mentioned. In addition, these polar monomers can be arbitrarily selected according to the purpose of use.

Preferred examples of the amino group-containing polar monomer in the polar monomer 1 include dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate. , Diethylaminomethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminomethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth)
Acrylamide, diethylaminomethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide,
One or more of vinyl pyridine and the like can be mentioned.
In addition, these polar monomers can be arbitrarily selected according to the purpose of use.

Preferred examples of the amide group-containing polar monomer in the polar monomer 1 include dimethyl (meth) acrylamide, diethyl (meth) acrylamide, isopropyl (meth) acrylamide, (meth) acryloylmorpholin, dimethylamino Methyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide,
One or more of diethylaminomethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide and the like can be mentioned. In addition, these polar monomers can be arbitrarily selected according to the purpose of use.

Polar monomer 2: A polar monomer represented by the following general formula (1).

The ^{_{CH 2 = CR 1 -COO- (CH}} 2 -CHR 2 -O) t -R 3 ·· (I)

[In the general formula (I), R ¹ and R ²
Is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ³ is an alkyl group having 1 to 5 carbon atoms or a phenyl group;
Is the number of repetitions and is an integer of 1 to 25. ]

Specifically, preferred polar monomers represented by the general formula (1) include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and 2-methoxypropyl (meth) acrylate. , 2-
Ethoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, methoxypolyethylene glycol (the number of units of ethylene glycol is 2 to 25) (meth)
Acrylate, ethoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (propylene glycol has 2 to 25 units) (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, phenoxypolypropylene glycol (meth) And acrylate and the like. In addition, these polar monomers can be arbitrarily selected according to the purpose of use.

Polar monomer 3: A polar monomer represented by the following general formula (2).

CH ₂ ＣＲCR ⁴ —COO— (C _m H _2m —CO
O) _n -R ⁵ ·· (2)

[In the general formula (2), R ⁴ has 1 carbon atom.
R ⁵ is an alkyl group having 1 to 10 carbon atoms or a phenyl group, n and m are the number of repetitions,
Each is an integer of 1 to 20. ]

Specifically, preferred polar monomers represented by the general formula (2) include CH ₂ ＣＨCH—COO—C ₃ H _{6
COO-H, CH 2 = C} (CH 3) -COO-C 3 H 6 CO
O—H, CH ₂ −CH—COO—C ₄ H ₈ COO—H, C
_{H 2 = C (CH 3)} -COO-C 4 H 8 COO-H, CH 2
_{= CH-COO-C 5 H} 10 COO-H, CH 2 = C (CH
_{3) -COO-C 5 H 10} COO-H, CH 2 = CH-CO
_{O-C 3 H 6 COO-} CH 3, CH 2 = C (CH 3) -CO
_{O-C 3 H 6 COO-} CH 3, CH 2 = CH-COO-C 4
_{H 8 COO-CH 3, CH} 2 = C (CH 3) -COO-C 4
_{H 8 COO-CH 3, CH} 2 = CH-COO-C 5 H 10 CO
_{O-CH 3, CH 2 =} C (CH 3) -COO-C 5 H 10 CO
_{O-CH 3, CH 2 =} CH-COO-C 3 H 6 COO-C 2
_{H 5, CH 2 = C (} CH 3) -COO-C 3 H 6 COO-C 2
_{H 5, CH 2 = CH-} COO-C 4 H 8 COO-C 2 H 5, C
_{H 2 = C (CH 3)} -COO-C 4 H 8 COO-C 2 H 5, C
_{H 2 = CH-COO-C} 5 H 10 COO-C 2 H 5, CH 2 =
_{C (CH 3) -COO-C} 5 H 10 COO-C 2 H 5, CH 2
_{= CH-COO-C 5 H} 10 COO-C 2 H 5, CH 2 = C
_{(CH 3) -COO-C 5} H 10 COO-C 2 H 5, CH 2 =
_{CH-COO-C 5 H 10} COO-C 4 H 9, CH 2 = C (C
_{H 3) -COO-C 5 H} 10 COO-C 4 H 9, CH 2 = CH
—COO—C ₅ H ₁₀ COO—C ₈ H ₁₇ , CH ₂ ＣC (C
_{H 3) -COO-C 5 H} 10 COO-C 8 H 17, CH 2 = CH
_{-COO- (C 3 H 6 COO)} 2 -H, CH 2 = C (C
_{H 3) -COO- (C 3 H} 6 COO) 2 -H, CH 2 = CH
_{-COO- (C 4 H 8 COO)} 2 -H, CH 2 = C (C
_{H 3) -COO- (C 4 H} 8 COO) 2 -H, CH 2 = CH
_{-COO- (C 5 H 10 COO)} 2 -H, CH 2 = C (C
_{H 3) -COO- (C 5 H} 10 COO) 2 -H, CH 2 = CH
_{-COO- (C 3 H 6 COO)} 2 -C 2 H 5, CH 2 = C (C
_{H 3) -COO- (C 3 H} 6 COO) 2 -C 2 H 5, CH 2 =
_{CH-COO- (C 4 H 8} COO) 2 -C 2 H 5, CH 2 = C
_{(CH 3) -COO- (C 4} H 8 COO) 2 -C 2 H 5, CH
_{2 = CH-COO- (C 5} H 10 COO) 2 -C 2 H 5, CH 2
_{= C (CH 3) -COO- (} C 5 H 10 COO) 2 -C
_{2 H 5, CH 2 = CH} -COO- (C 5 H 10 COO) 3 -C 2
_{H 5, CH 2 = C (} CH 3) -COO- (C 5 H 10 COO)
_{3 -C 2 H 5, CH 2} = CH-COO- (C 5 H 10 COO) 4
_{-C 2 H 5, CH 2 =} C (CH 3) -COO- (C 5 H 10 C
_{OO) 4 -C 2 H 5,} CH 2 = CH-COO- (C 5 H 10 C
_{OO) 5 -C 2 H 5,} CH 2 = C (CH 3) -COO- (C 5
_{H 10 COO) 3 -C 2 H} 5, CH 2 = CH-COO- (C 5
_{H 10 COO) 5 -C 2 H} 5, CH 2 = C (CH 3) -COO
_{- (C 5 H 10 COO)} 2 -C 8 H 17, CH 2 = CH-COO
One or more of — (C ₅ H ₁₀ COO) ₂ —C ₈ H _{17 and the} like. In addition, these polar monomers can be arbitrarily selected according to the purpose of use.

Next, the content of the above-mentioned polar monomer in the segment A will be described. In the present invention, the content of the polar monomer needs to be a value within a range of 10 to 100 mol%, and more preferably a value within a range of 20 to 100 mol%. When the content of the polar monomer is less than 10 mol%, the polarity of the segment A is low, and the affinity for the swelling ester compound is reduced,
This is because the swelling ratio due to the ester compound may be reduced.

The constituent components other than the above-mentioned polar monomers 1 to 3 in the segment A are not particularly limited. For example, polymerization of (meth) acrylate, conjugated diene compound, vinyl aromatic compound, etc. It is preferable to use a hydrophilic monomer.

Specifically, preferred (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate,
One or more of tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and the like can be mentioned. In particular, it is preferable to use methyl (meth) acrylate, ethyl (meth) acrylate, or n-butyl (meth) acrylate because affinity with the ester compound is further improved and the degree of swelling with respect to the block copolymer increases.

More specifically, preferred conjugated diene compounds include, for example, 1,31-butadiene, isoprene,
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3
One kind or two or more kinds of monohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like can be mentioned. In order to obtain a polymer having higher industrial utility and better physical properties, it is more preferable to use 1,31-butadiene, isoprene, and 1,3-pentadiene.
3 Use of butadiene and isoprene.

Specifically, preferred vinyl aromatic compounds include, for example, styrene, α-methylstyrene,
One or more kinds of o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene and the like can be mentioned. In particular, in order to obtain a polymer having high industrial utility and superior physical properties, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt
It is preferred to use tert-butylstyrene.

(2) Segment B The segment B forms a domain as a physical crosslinking point in the block copolymer, and has a function of improving the mechanical strength of the block copolymer. Therefore, the content of the first to third polar monomers in the segment B needs to be less than 10 mol%. This is because the polar monomer content is 10 mol%.
This is because the above may cause a decrease in the mechanical strength of the block copolymer composition. More specifically, when the content of the polar monomer in the segment B is 10 mol% or more, not only the segment A but also the segment B
This is because the affinity of the ester compound also increases, and the entire block copolymer is plasticized by the ester compound. Therefore, the content of the polar monomer in the segment B is more preferably less than 5 mol%.

The polar monomer 1 in segment B
Although there is no particular limitation on the components other than the components 3 to 3, the same components as those in the segment A, for example,
It is preferable to use polymerizable monomers such as (meth) acrylates, conjugated diene compounds, and vinyl aromatic compounds.

Specifically, preferred (meth) acrylates are methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate,
One or more of tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and the like can be mentioned.

More specifically, preferred conjugated diene compounds include, for example, 1,31-butadiene, isoprene,
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3
One kind or two or more kinds of monohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like can be mentioned.

Specifically, preferred vinyl aromatic compounds include, for example, styrene, α-methylstyrene,
One or more kinds of o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene and the like can be mentioned. In addition, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methyl styrene, from the viewpoint of particularly excellent shape retention of the composition after swelling the ester compound and obtaining higher mechanical properties. It is preferable to use methyl styrene and p-tert-butyl styrene.

(3) Connection state of segment A and segment B Next, the connection state of segment A and segment B will be described. The bonding state of the segment A and the segment B is not particularly limited, but, for example, contains 10 to 100% by mole of at least one polar monomer selected from polar monomers 1 to 3 as a constituent component. A (abbreviated as A) and segment B (abbreviated as B) in which the content of the polar monomer is less than 10 mol%.
Are preferably (A)-(B) block copolymers bonded to each other. In addition, segment A (A), segment (B), and polar monomer 1 within a range of less than 10 mol%.
(B)-(A)-consisting of a tapered block segment (abbreviated as C) in which the content of ３3 gradually decreases.
(C) Block copolymers are also preferred. Furthermore, segment B (B), segment A (A), and segment B
A (B)-(A)-(B) block copolymer or the like formed in this order from (B) is also preferable.

Further, the above (A)-(B) block copolymer, (B)-(A)-(C) block copolymer,
Each of the (B)-(A)-(B) block copolymers is represented by the following general formula (3)-
It is also preferable to use a block copolymer having an extended or branched segment as represented by (5).

[(B)-(A)] _p -X (3)

[In the general formula (3), p represents an integer of 2 to 4, and X represents a residue of a coupling agent. ]

[(B)-(A)-(C)] _p -X (4)

[In the general formula (4), p represents an integer of 2 to 4, and X represents a residue of a coupling agent. ]

[(B) − (A) − (B)] _p− X (5)

[In the general formula (5), p represents an integer of 2 to 4, and X represents a residue of a coupling agent. ]

(4) Ratio of Segment A and Segment B Next, the ratio of segment A and segment B in the block copolymer will be described. Although the ratio of the segment A and the segment B is not particularly limited, the weight of the entire block copolymer is 10
When the weight is 0% by weight, the weight of the segment A is 20 to 9%.
The value is preferably in the range of 0% by weight, more preferably in the range of 30 to 85% by weight.
If the weight of the segment A is less than 20% by weight, the affinity of the block copolymer for the ester compound may decrease, and as a result, the degree of swelling in the block copolymer composition may decrease.
Therefore, when the block copolymer composition is stored for a long period of time, the ester compound may exude. On the other hand, when the weight of the segment A exceeds 90% by weight, the weight of the segment B is relatively reduced, the mechanical strength of the block copolymer composition is reduced, and the shape retention may be reduced. .

The weight of the segment B is preferably in the range of 10 to 80% by weight, more preferably 25 to 70% by weight, when the total weight of the block copolymer is 100% by weight. Is a value within the range. If the weight of the segment B is less than 10% by weight, the mechanical strength of the block copolymer composition is reduced, and the shape retention may be reduced.
On the other hand, if the weight exceeds 80% by weight, the weight of the segment A is relatively reduced, and the affinity of the block copolymer for the ester compound may be reduced.

As described above, by configuring the ratio of the segment A and the segment B as described above, the mechanical strength of the block copolymer composition and the affinity for the ester compound can be exhibited in a well-balanced manner.

(5) Molecular Weight Next, the polystyrene reduced number average molecular weight (hereinafter simply referred to as molecular weight or Mn) of the block copolymer will be described. The number average molecular weight in terms of polystyrene (hereinafter referred to as [Mn]) of the block copolymer is 5.00
It is preferable to set the value in the range of 0 to 5,000,000. If the molecular weight of the block copolymer is less than 5,000, the shape retention of the block copolymer composition may be reduced when an ester compound is added to the block copolymer. on the other hand,
If the molecular weight of the block copolymer exceeds 5,000,000, the processability of the space for processing the block copolymer may deteriorate or the affinity with the ester compound may decrease.

Accordingly, the molecular weight of the block copolymer is more preferably in the range of 7,000 to 2,000,000 from the viewpoint of better balance between the shape retention of the block copolymer composition and processability. And, optimally, 10,000 to 1,000,
000. The molecular weight of the block copolymer is determined by measuring the elution time of the block copolymer from the column using a GPC (gel permeation chromatography) apparatus, and comparing the elution time with a calibration curve (elution time) prepared in advance in standard polystyrene. And the molecular weight).

(6) Production Method Next, a method for producing a block copolymer will be described. Although the method for producing the block copolymer is not particularly limited, for example, the following methods (a) to (d) can be employed.

(A) Segment A or segment B
A method of synthesizing one of the above and subsequently synthesizing the other to produce a block copolymer. (B) A method in which a segment A and a segment B are separately synthesized, and then combined by a coupling reaction to produce a block copolymer. (C) A method for producing a block copolymer by synthesizing a segment B using a polymerization initiator having a segment A structure in a molecule. (D) A method for producing a block copolymer by synthesizing a segment A using a polymerization initiator having a segment B structure in a molecule.

It is to be noted that the control of the block structure and the control of the molecular weight in each segment are easier, and the block copolymer can be synthesized in one reaction vessel. The method (a) above, which is a method of synthesizing the compound and subsequently synthesizing the other, is more preferable. This (a)
More specifically, it is preferable to employ living anionic polymerization, living cationic polymerization, living radical polymerization or the like in order to carry out the above method.

The block copolymer used in the block copolymer composition of the present invention is produced by polymerizing a functional group-containing monomer or a polar monomer.
As a production method, living radical polymerization which is not affected by these functional groups and the like is more preferable.

As the living radical polymerization, an atom transfer living radical polymerization method using an organic halogen compound, copper halide and 2,2-pyridine can be exemplified as a more preferable production method (J. Am. C.).
hem. Soc., 114, 5614 (1995) and Macromolecules, 28, 7901
(1995)).

2. Ester Compound The block copolymer composition of the present invention is configured to include an ester compound (which may be broadly referred to as an ester compound) as the second component.

Here, the ester compound of the second component is not particularly limited, but is preferably liquid at the use temperature (for example, 25 ° C.) from the viewpoint of good usability and the like.

Preferred types of ester compounds include, for example, methyl acetate, ethyl acetate,
Acetates such as isopropyl acetate and n-butyl acetate; propionates such as methyl propionate, ethyl propionate and butyl propionate; methyl acetoacetate, ethyl acetoacetate and te
acetoacetates such as rt-butyl acetoacetate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tert
Alkyl (meth) acrylates such as -butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate and lauryl (meth) acrylate; methyl crotonic acid, ethyl crotonic acid, n crotonic acid Unsaturated monocarboxylic acid esters such as monopropyl, n-butyl crotonate, ethyl cinnamate, n-propyl cinnamate and n-butyl cinnamate; ethylene glycol, 1,2-propanediol, 3-chloro -1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc. Mono- or di- (meth) acrylates of alkylene glycols; Mono- or di- (meth) acrylates of polyalkylene glycol (alkylene glycol units having 2 to 25) such as propylene glycol; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxy Alkoxyalkyl (meth) acrylates such as propyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, 31-methoxypropyl (meth) acrylate, and 31-ethoxypropyl (meth) acrylate; methoxypolyethylene glycol, ethoxypolyethylene glycol, Alkoxy polyalkylene glycols such as methoxy polypropylene glycol and ethoxy polypropylene glycol (the number of alkylene glycol units is 2 to 2)
5) (meth) acrylates; aryloxyalkyl (meth) acrylates such as 2-phenoxyethyl (meth) acrylate, 2-phenoxypropyl (meth) acrylate, and 3-phenoxypropyl (meth) acrylate; phenoxypolyethylene glycol; Aryloxy polyalkylene glycols such as phenoxy polypropylene glycol (the number of alkylene glycol units is 2 to 2)
25) mono (meth) acrylates; 2-cyanoethyl (meth) acrylate, 3-cyanopropyl (meth)
Cyanoalkyl (meth) acrylates such as acrylate; 2- (2-cyanoethoxy) ethyl alcohol;
-(2-cyanoethoxy) propyl alcohol, 4- (21-cyanoethoxy) butyl alcohol, 2- [2-
(2-cyanoethoxy) ethoxy] cyanoalkoxyalkyl (meth) acrylates such as ethyl alcohol;
Trivalent or higher polyvalent such as glycerin, 1,2,4-butanetriol, pentaerythritol, trimethylolalkane (alkane has 1 to 3 carbon atoms), tetramethylolalkane (alkane has 1 to 3 carbon atoms) Mono- or oligo- (meth) acrylates of alcohols; mono- or oligo- (meth) acrylates of polyalkylene glycol adducts of the trihydric or higher polyhydric alcohol; 1,4-cyclohexanediol, Mono- or oligo (meth) acrylates of cyclic diols such as 1,4-benzenediol and 1,4-dihydroxyethylbenzene; ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate
Carbonate, methyl isopropyl carbonate, diethyl carbonate, ethyl propyl carbonate, ethyl isopropyl carbonate, propylene carbonate, dipropyl carbonate, diisopropyl carbonate,
Carbonates such as butylene carbonate; β-butyrolactone, γ-butyrolactone, γ-caprolactone;
Lactones such as ε-caprolactone. These ester compounds can be used alone or as a mixture of two or more.

The ratio (addition amount) of the above-mentioned ester compound in the block copolymer composition of the present invention is
The value is preferably within the range of 10 to 1000 parts by weight based on 100 parts by weight of the block copolymer as the first component. If the ratio of the ester compound is less than 10 parts by weight, the properties (effect) of the ester compound in the block copolymer composition may not be sufficiently obtained. This is because the mechanical strength of the composition may be significantly reduced.

Accordingly, from the viewpoint of better balance between the effect of adding the ester compound and the mechanical strength of the block copolymer composition, the ratio (addition amount) of the ester compound is set to 20 to 700 weight parts per 100 weight parts of the block copolymer. It is more preferable that the value be within the range of parts.

3. Other Additives In addition to the above-described first and second components, the following third component can be added to the block copolymer composition of the present invention.

(1) Radical generator For the purpose of imparting properties according to the application to the block copolymer composition of the present invention, a heat radical generator or a photo radical generator can be added and blended. That is, for example, when various (meth) acrylates are used as the ester compound, crosslinking can be performed by heat or light (ultraviolet light, visible light, or the like) by adding a generator or a photoradical generator. It can be used as a thermosetting or photocurable block copolymer composition.

Preferred thermal radical generators include, for example, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane as an organic peroxide.
Di-tert-butyl peroxide, tert-butyl cumyl peroxide, di-cumyl peroxide,
2,5-di-methyl-2,5-di (tert-butylperoxy) hexane), 2,5-di-methyl-2,5-
Di (tert-butylperoxy) hexyne, 1,3 bis- (tert-butylperoxy-iso-propyl)
Benzene, tert-butyl peroxy-iso-propyl carbonate, acetylcyclohexylsulfonyl peroxide, iso-butyl peroxide, di-isopropyl peroxy dicarbonate, di-allyl peroxy dicarbonate, di-n-propyl peroxy dicarbonate , Di- (2-ethoxyethyl) peroxydicarbonate, di (methoxyisopropyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, tert-hexylperoxyneohexanate, di (3-methyl- 3-methyloxybutyl) peroxydicarbonate, tert-butylperoxyneodecanate, tert-hexylperoxyneodecanate, tert-butylperoxyneohexanate, 2,4- Chlorobenzoyl peroxide,
tert-hexyl peroxypivalate, tert-butyl perhexopivalate, 3,3,5-trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, cumylperoxyoctate, acetyl peroxide Tert-butylperoxy (2-ethylhexanate), benzoyl peroxide, tert-butylperoxyisoisobutyrate, 1,1-bis (t
tert-butylperoxy) cyclohexane, tert
-Butylperoxymaleic acid, tert-butylperoxylaurate, tert-butylperoxy-3,3,5-trimethylhexanate, cyclohexanone peroxide, tert-butylperoxyallylcarbonate, 2,5-dimethyl- 2,5-di (benzoylperoxy) hexane, 2,2-bis (ter
t-butylperoxy) octane, tert-butylperoxyacetate, 2,2-bis (tert-butylperoxy) butane, tert-butylperoxybenzoate, n-butyl-4,4-bis (tert-butylpert Oxy) valerate, di-tert-butyldiperoxyisophthalate, methyl ethyl ketone peroxide, α, α′-bis (tert-butylperoxy-m-isopropyl) hexane, di-isopropylbenzene-hydroperoxide, p-methane Hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5, -dimethylhexane-2,5
-Dihydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide and the like. These can be used alone or as a mixture of two or more. It is also preferred that a polyfunctional unsaturated compound or the like be used in combination with the organic peroxide as a crosslinking aid.

Preferred photo-radical generators include α-diketone compounds such as diacyloyl and benzyl which are usually used as photosensitizers; benzoin,
Acyloins such as pivaloin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether; anthraquinone;
Polynuclear quinones such as 1,4-naphthoquinone; benzophenones such as 2,2-dimethoxyphenylacetophenone and methyl-o-benzoylbenzoate;
These can be used alone or as a mixture of two or more.

(2) Polymerization Inhibitor When used as the above-described thermosetting or photocurable block copolymer composition, a polymerization inhibitor may be blended within a range that does not impair the effects of the present invention. By using the polymerization inhibitor, the thermosetting property or the photocuring property can be easily controlled, and the storage stability of the block copolymer composition can be remarkably improved.

Preferred polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, mono-t-butylhydroquinone, catechol, p-methoxyphenol, p-tert-butylcatechol, 2,6-di-t-t
ert monobutyl-p-cresol, 2,8-di-ter
quinones such as t-butyl-m-cresol, pyrogallol, β-naphthol; nitrobenzene, m-dinitrobenzene, 2-methyl-2-nitrosopropane, α-phenyl-tert-butylnitrone, 5,5-1-dimethyl-
Nitro compounds or nitrone compounds such as 1-pyrroline-l-oxide; chloranyl-amine, diphenylamine, diphenylpicrylhydrazine, phenol-α-
Amines such as naphthylamine, pyridine and phenothiazine; sulfides such as dithiobenzoyl sulfide and dibenzyltetrasulfide; unsaturated compounds such as 1,1-diphenylethylene, α-methylthioacrylonitrile; and thionin blue, toluidine blue and methylene blue Thiazine dye; 1,1-diphenyl-2-picrylhydrazyl, 1,3,5-triphenylferdazyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 2,6 1-di-tert-butyl-α- (3,5-di-tert-butyl) -1-oxo-2,5-cyclohexadiene-1-ylidene-p-
And stable radicals such as trioxyl. These polymerization inhibitors can be used alone or as a mixture of two or more.

(3) Electrolyte (Salt) When the block copolymer composition of the present invention is used as a solid electrolyte in an electrochemical device such as a lithium secondary battery, it is necessary to add an electrolyte (salt). The electrolyte varies depending on the use of the solid electrolyte to be manufactured. For example, in consideration of application to a lithium secondary battery, preferred electrolytes include LiClO ₄ , LiAlCl ₄ ,
LiBF ₄ , LiPF ₄ , LiNbF ₆ , LiAsF
₆ , LiSCN, LiCl, Li (CF ₃ SO ₃ ), Li
(C ₄ F ₉ SO ₃ ), Li (CF ₃ SO ₂ ) ₂ N, LiI,
LiCl, lithium salt of Li (C ₆ H ₅ SO ₃ ); Na
Examples thereof include alkali metal salts such as BF ₄ , ammonium benzoate, and ammonium tartrate, and alkaline earth metal salts. These electrolytes can be used alone or as a mixture of two or more.

It is preferable that the concentration of the electrolyte dissolved in the solvent is in the range of 0.001 to 5 mol / L. If the concentration of the electrolyte is outside this range, the charge / discharge characteristics of the electrochemical device may be deteriorated.

4. Next, a method for producing the block copolymer composition according to the present invention will be described. The method for producing the block copolymer composition is not particularly limited, but for example, the following production method can be adopted.

(1) The first component (block copolymer), the second component (ester compound) and, if necessary, additives are sufficiently stirred and mixed using a kneader, an intermixer or the like, and the block copolymer composition is obtained. Manufacturing things. (2) Using a kneader, an intermixer, etc., thoroughly mix and stir the first component (block copolymer) and, if necessary, additives, etc., then mold, and then add the second component (ester compound). By doing so, a block copolymer composition is produced.

(3) The first component (block copolymer) and, if necessary, additives are dissolved in an organic solvent, then cast on a substrate, and the organic solvent is removed by a reduced pressure operation or the like to obtain a cast film. Then, this cast film,
The block copolymer composition is manufactured by immersing in the second component (ester compound) or the second component (ester compound) component (2) mixed with additives as necessary. (4) When various (meth) acrylates are used as the ester compound, a block copolymer composition obtained by further blending a generator or a photo-radical generator and then performing crosslinking by heating or irradiation with light is used. To manufacture.

[0081]

The present invention will be described below in more detail with reference to examples. However, the following description is only a general description of the present invention, and the present invention is not limited to the following description without any particular reason.

In the following description, ST as the type of monomer is styrene, BA is n-butyl acrylate, HEA is 2-hydroxyethyl acrylate, ED
EA is ethoxydiethylene glycol acrylate, A
N represents acrylonitrile. EGMA as an ester compound is ethylene glycol dimethacrylate, PC is propylene carbonate, γ
-BL represents γ-butyrolactone, respectively. Also, M
n represents the number average molecular weight in terms of polystyrene, Mw represents the weight average molecular weight in terms of polystyrene, and each was measured using gel permeation chromatography (hereinafter, referred to as GPC). Further, in the following description, “parts” means “parts by weight” unless otherwise specified.

[Synthesis Example 1] (Synthesis of segment A) A 1000 ml separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube and a stirrer was replaced with nitrogen, and copper (I) bromide was added to the flask. 06 g,
9.96 g of 2,2-bipyridine, 2.8 g of α, α′-dibromo-p-xylene, 200 g of diphenyl ether,
Each 200 g of EDEA was stored. Then, the separable flask containing these reaction mixtures was placed in a nitrogen stream at 90 ° C. using an oil bath while stirring.
To polymerize the EDEA as a monomer.

During the polymerization, a reaction mixture containing EDEA was appropriately withdrawn and diluted with tetrahydrofuran to prepare a diluent. The diluted solution is subjected to gas chromatography (hereinafter, referred to as GC) according to a conventional method.
Was used to measure the consumption of the EDEA (monomer), and the polymerization conversion was calculated. And, the polymerization conversion rate of EDEA is 9
When it reached 3%, the separable flask was cooled and the polymerization of segment A was terminated. When the molecular weight of the obtained segment A was measured using GPC, Mn was 1
Mw / Mn which is 4,000 and is a standard of molecular weight distribution.
Was 1.3.

(Synthesis of Block Polymer) To the separable flask containing the above reaction mixture, 200 g of ST was further added as a segment B component, followed by heating at a temperature of 90 ° C. to polymerize ST and obtain a monomer as ST. The remaining EDEA was polymerized. And E
The polymerization conversion of DEA is 97% and the polymerization conversion of ST is 63
%, The separable flask containing the reaction mixture was cooled to terminate the polymerization. Next, the reaction mixture was poured into n-hexane, and the resulting precipitate was filtered and dried under reduced pressure to obtain a block polymer (P-1).

When the molecular weight of the obtained P-1 was measured by using GPC, the Mn was 23,000 and the Mw was
/ Mn was 1.5. In addition, since the molecular weight distribution remains unimodal (one peak) and the molecular weight is higher than that of segment A, block polymerization proceeds, and a triblock polymer of segment B-segment A-segment B is obtained. It is estimated that From the consumption of each monomer determined by GC, the monomer composition of segment B is ST / EDEA = 96/4 (mol%),
The ratio of segment A to segment B is A / B = 58 /
42 (wt%) was obtained. Table 1 shows the composition and molecular weight (Mn, Mw / Mn) of the obtained block copolymer.

[0087]

[Table 1]

[Synthesis Examples 2 to 4] The same procedure as in Synthesis Example 1
Under the conditions, BA / HEA (Synthesis Example 2, charge ratio 790)
/ 21 mol%) or copolymerization of BA / EDEA (Synthesis Example 3, charging ratio 550/45 mol%) or E
Homopolymerization of DEA (Synthesis Example 4, charge ratio 100 mol)
%). The molecular weight (Mn, Mw / Mn) as the segment A obtained at this time was measured in the same manner as in Synthesis Example 1. Table 1 shows the measurement results. Next, ST is further added, and block polymerization of segment B is performed under the same procedure and conditions as in Synthesis Example 1, and block copolymers (P-2), (P-3) and (P-
4) was obtained. The molecular weight of the obtained block copolymer is
It was measured using GPC in the same manner as in Synthesis Example 1, and further, G
The composition ratio was measured using C. Table 1 shows the measurement results.

[Synthesis Examples 5 to 6] The same procedure as in Synthesis Example 1
BA / AN (Synthesis example 5) or ST / AN
After polymerization of segment A comprising (Synthesis Example 6),
A vacuum pump was connected to the separable flask, and unreacted monomers were removed under reduced pressure. Segment A obtained at this point
(Mn, Mw / Mn) was measured in the same manner as in Synthesis Example 1. Table 1 shows the measurement results. Next, ST was further added, and block polymerization of segment B was performed under the same procedures and conditions as in Synthesis Example 1, to obtain block copolymers (P-5) and (P-6). Further, in the same manner as in Synthesis Example 1, the molecular weight of the obtained block copolymer was measured using GPC, and further, the composition ratio was measured using GC. Table 1 shows the measurement results.

[Synthesis Example 7] A 1000 ml separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube and a stirrer was purged with nitrogen, and 0.38 g of azobisisobutyronitrile (AIBN) and 563 g of toluene were added thereto. , BA1
52.5 g and 34.5 g of HEA were respectively accommodated. Then, the separable flask containing the reaction mixture was heated to 60 ° C. using an oil bath while stirring under a nitrogen stream, and BA and HE as monomers were heated.
The polymerization of A was carried out for 10 hours.

Next, the consumption of the monomer was determined using GC, and the polymerization conversion of the monomer was calculated. As a result, a value of 90% was obtained. The monomer composition of the polymer determined from the consumption of the monomer was BA / HEA = 79/21.
Further, the obtained reaction mixture was poured into n-hexane, and the resulting precipitate was filtered and dried under reduced pressure to obtain a random cobolimer (P-7). When the molecular weight was measured using GPC, Mn was 72,000, and Mw / M
n was 3.4.

Example 1 (Preparation of Block Copolymer Composition) The block copolymer (P-1) synthesized in Synthesis Example 1 was dissolved in toluene to prepare a 10% by weight polymer solution. This polymer solution was spread on a Teflon dish and dried at normal temperature and normal pressure for 8 hours. Thereafter, the film was further dried at 30 ° C. under reduced pressure for 10 hours to obtain a cast film. This cast film was immersed and swelled in γ-BL as an ester compound for 24 hours to obtain a target block copolymer composition of the present invention.

(Evaluation of Block Copolymer Composition) The degree of swelling, liquid retention, and shape retention characteristics of the block copolymer composition were measured by the following methods.

(1) Degree of swelling in the block copolymer composition From the weight after swelling and the weight before swelling after immersing the cast film of the block polymer in the ester compound for 24 hours, the degree of swelling in the block copolymer composition is calculated using the following formula. Was calculated. Table 2 shows the measurement results. Swelling degree (%)
= [Weight after swelling (g)-weight before swelling (g)] / weight after swelling (g) x
100

(2) Liquid Retaining Property of Block Copolymer Composition A cast film immersed in an ester compound for 24 hours was left in a glass petri dish, and after swelling for 10 hours, the weight was measured. Then, from the weight after swelling before and after the elapse of 10 hours, the degree of swelling as liquid retention was measured using the above formula. Table 2 shows the measurement results.

(3) Shape Retention in the Block Copolymer Composition From the appearance of the cast film immersed in the ester compound for 24 hours, the shape retention in the block copolymer composition was determined according to the following criteria. Table 2 shows the judgment results.
Shown in It should be noted that if the shape retention is excellent, it can be said that the block copolymer composition is also excellent in mechanical strength. X: It dissolves in the ester compound and cannot maintain a certain shape. Δ: Despite maintaining a constant shape in the ester compound, it undergoes plastic deformation when elongated. 〇: Retains a constant shape in the ester compound, exhibits rubber elasticity even when elongated, and returns to the original shape.

As can be easily understood from the results shown in Table 2, the block copolymer composition of the present invention has a high swelling degree of 87% or more, and has a liquid retention of 73% or more. It was also confirmed that the shape retention characteristics were excellent.

[0098]

[Table 2]

Examples 2 to 4 (Preparation of Block Copolymer Composition) A block copolymer composition was prepared in the same manner as in Example 1 using the ester compounds shown in Table 2. That is,
In Example 2, a block copolymer composition was prepared using the block copolymer (P-2) and PC as the ester compound. In Example 3, a block copolymer composition was prepared using the block copolymer (P-3) and EG as an ester compound. Further, in Example 4, the block copolymer (P-5)
Using EG as an ester compound, a block copolymer composition was prepared.

(Evaluation of Block Copolymer Composition) In the same manner as in Example 1, the degree of swelling, liquid retention, and shape retention properties of the block copolymer composition were measured. Table 2 shows the measurement results. As can be easily understood from the results shown in Table 2, the block copolymer compositions of the present invention (Examples 2 to 4) all have a high degree of swelling of 75% or more, although they slightly vary depending on the type of the ester compound used. showed that. In addition, all of the liquid retention properties showed a high value of 62% or more, and further, it was confirmed that the shape retention properties were also excellent.

[Comparative Examples 1 to 3] (Preparation of Block Copolymer Composition) Block copolymer compositions were prepared in the same manner as in Example 1 using the ester compounds shown in Table 2. That is,
In Comparative Example 1, a block copolymer composition was prepared using the block copolymer (P-4) and γ-BL as an ester compound. In Comparative Example 2, the block copolymer (P-6) and E as an ester compound were used.
G was used to make a block copolymer composition.
Further, in Comparative Example 3, the block copolymer (P-7)
And a PC as an ester compound to prepare a block copolymer composition.

(Evaluation of Block Copolymer Composition) In the same manner as in Example 1, the degree of swelling, liquid retention, and shape retention characteristics of the block copolymer composition were measured. Table 2 shows the measurement results. As can be easily understood from the results shown in Table 2, in Comparative Example 1, the polymer was dissolved in γ-BL as an ester compound, and did not become a swellable composition. Could not be held. The reason for this is that the polymer (P
It is presumed that, since the amount of use of EDEA in segment B of -4) is too large, affinity with γ-BL as an ester compound is improved, and segment B itself dissolves in γ-BL. In addition, in Comparative Example 1, (-) is described in the corresponding portion to indicate that the swelling degree and the liquid retaining property in Table 2 could not be measured.

In Comparative Example 2, the polymer (P-6)
This is probably because the content of AN in segment A is small, but the composition does not have a large swelling degree due to poor affinity with EG as an ester compound. further,
In Comparative Example 3, the random copolymer (P-7) was dissolved in PC as an ester compound, the composition did not become a swellable composition, and a constant shape could not be maintained from the initial stage. Therefore, for Comparative Example 3, Table 2
In order to show that the swelling degree and the liquid retention property of the sample could not be measured, (-) is described in the corresponding portion.

[0104]

As described above, the block copolymer composition of the present invention comprises:
By using a specific polar monomer and a specific amount, it is possible to provide a block copolymer composition having an excellent balance between swelling degree and the like, which were conventionally considered to be contradictory properties, and mechanical strength. It became so. That is, it has become possible to provide a block copolymer composition which has a high degree of swelling with respect to the ester compound and is excellent in liquid retention properties, but also has excellent mechanical strength and shape retention properties.

Therefore, the block copolymer composition of the present invention can be used very suitably as a solid electrolyte material which is adjusted by swelling with an organic solvent in which a metal salt is dissolved.

The block copolymer composition of the present invention can be produced simply by preparing a block copolymer using ordinary solution polymerization or the like, and then adding an ester compound. There is no need to process the molecules at a high temperature, and the production of a solid electrolyte or the like for a lithium secondary battery using the block copolymer composition has become extremely easy.

Further, by using an ester compound having a polymerizable unsaturated bond and a suitable polymerization initiator, a thermosetting or photocurable composition can be obtained. Therefore, the composition can be widely used for paints, adhesives, printed boards, molding materials, and the like.

Claims (2)

[Claims] (1) at least one polar monomer selected from the group consisting of the following polar monomer 1, the following polar monomer 2, and the following polar monomer 3 as a constituent component;
Segment A containing 0 mol% and segment B containing less than 10 mol% as a constituent of the polar monomer
A block copolymer composition comprising a block copolymer consisting of: and (2) an ester compound. Polar monomer 1: a polar monomer having at least one polymerizable unsaturated bond and at least one functional group selected from the group consisting of a hydroxy group, a nitrile group, a carboxyl group, an amino group and an amide group. Body. Polar monomer 2: a polar monomer represented by the following general formula (1). CH ₂ ＣＲCR ¹ —COO— (CH ₂ —CHR ² —O) _t —R ³ ... (I) [In the general formula (I), R ¹ and R ² are each a hydrogen atom or a carbon atom having 1 to 5 carbon atoms. The alkyl group, R ³ is an alkyl group having 1 to 5 carbon atoms or a phenyl group, and t is the number of repetitions, and is an integer of 1 to 25. Polar monomer 3: A polar monomer represented by the following general formula (2). CH ₂ ＣＲCR ⁴ —COO— (C _m H _2m —COO) _n —R ⁵ (2) [In the general formula (2), R ⁴ is an alkyl group having 1 to ⁵ carbon atoms, and R ⁵ is a carbon number. 1 to 10 alkyl groups or phenyl groups, n and m are the number of repetitions and are integers of 1 to 20. ] 2. The block copolymer composition according to claim 1, wherein the segment B contains a styrene compound as a main component.