TW201920384A - Block copolymer, resin composition, coating, resin film, OLED element, light emitting device, and manufacturing method for block copolymer - Google Patents

Abstract

The present invention provides a novel block copolymer having a urea bond or a urethane bone in the molecule thereof, and having excellent transparency, heat resistance, and mechanical properties. The present invention is a block copolymer that is a polyaddition copolymer of alternating copolymers 1 and 2 and that includes repeating units represented by formula (3). Formula (3): -[(alternating copolymer 1)-(alternating copolymer 2)]-. (In formula (3), alternating copolymer 1 is a polyaddition copolymer of diisocyanate <A> and diamine <B>, alternating copolymer 1 being a polyurea-based alternating copolymer including repeating units represented by formula (1) (-[(A)-(B)-]-). Alternating copolymer 2 is a polyaddition copolymer of diisocyanate <A> and diamine <C1> or diol <C2>, alternating copolymer 2 being a polyurea-based alternating copolymer 2-1 or a polyurethane-based alternating copolymer 2-2 including repeating units represented by formula (2-1) (-[(A)-(C1)-]-) or formula (2-2) (-[(A)-(C2)-]-)).

Description

Block copolymer, resin composition, coating film, resin film, OLED element, light-emitting device, and method for producing block copolymer

The present invention relates to a novel urea-based or urethane-based novel block copolymer useful in the field of flexible device in the field of electronic information materials, and useful as a highly elastic recovery material, and its production. method. Furthermore, it relates to a material that can be applied horizontally to various applications such as automobiles, building materials, and life sciences.

In recent years, the popularity of liquid crystal display (LCD) terminals that can be carried and can be used outdoors has been remarkable. Examples include smartphones and personal navigation devices (PNDs). Mobile terminal, or wearable display represented by Google Glass. Furthermore, with the practical use of organic electroluminescence (EL) displays, further weight reduction is required, and a method of changing a part of a member from glass or thin film glass to plastic is required. However, although film glass is excellent in heat resistance, it is very easy to crack on the other hand. Plastic (especially polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate) Polymethyl methacrylate (PMMA, cyclic olefins, etc.) has the characteristics of light weight and high transparency, but sometimes lacks mechanical properties such as impact resistance and damage resistance, so the development of a new type of functional plastic is required.

Patent Document 1 discloses a coating agent having excellent scratch resistance for glass substrates, and excellent adhesion to glass and scattering resistance (paragraph 0019). However, although the obtained glass coating layer is excellent in scratch resistance and scattering resistance, it is not sufficient when it is used for recent smartphones or wearable displays. On the other hand, Patent Document 2 discloses a novel polyurea resin which has various rollers and casters other than calender rolls used in papermaking, fabrics, magnetic tapes, and the like. High general hardness and toughness useful for general molding resins, as well as excellent heat resistance (paragraph 0001). However, this technology is related to a general molding resin used for injection into a mold, and is not intended to be applied to a film-like mobile terminal or the like in terms of handling and the like. Furthermore, Patent Document 3 discloses a composition for a polyfluorene iminosiloxane-based insulating film, which can be obtained by performing a heat treatment at a low temperature, has good adhesion to a substrate or a sealing material, and has improved properties. Tin plating resistance, and further less warpage, excellent heat resistance, solder resistance, solvent resistance, chemical resistance, bending resistance, and electrical characteristics, and can be used on substrates such as flexible wiring boards. Coated and used to form insulating films for electrical and electronic parts. However, this technology is assumed to be applied to a flexible wiring substrate, and no consideration is given to the transparency required for display applications. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open No. 2006-290696 [Patent Literature 2] Japanese Patent Laid-Open No. 5-194695 [Patent Literature 3] Japanese Patent Laid-Open No. 2004-231757

[Problems to be Solved by the Invention]

An object of the present invention is to provide a novel block copolymer having a urea bond or a urethane bond in the molecule, and a method for producing the same, which have particularly excellent properties of transparency, heat resistance, and mechanical properties.

Furthermore, since the novel block copolymer of the present invention has an amine or an isocyanate at the molecular terminal and a urea structure or a urethane structure in the molecule, it can be used, for example, with a (meth) acrylate having an isocyanate group or having a cyclic group. The oxy (meth) acrylate reacts, and introduction of a vinyl-based functional group can be easily performed. [Means for solving problems]

The present inventors have conducted diligent research in order to achieve the above-mentioned object, and as a result, have discovered that an additive polymerization reaction of an aliphatic diisocyanate compound <A> and a diamine compound <B> having a cyclic structure in the molecule is obtained Alternating copolymers 1. Alternating copolymers with addition polymers as aliphatic diisocyanate compounds <A> having a cyclic structure in the molecule and specific diamine compounds <C ¹ > or diol compounds <C ² > 2 A block copolymer obtained by further addition polymerization and a method for producing the same, thereby completing the present invention. Examples of aspects of the present invention are shown below.

[1] A block copolymer, which is an addition polymerization copolymer of the following alternating copolymer 1 and the following alternating copolymer 2, and includes a repeating unit represented by formula (3), and has a weight average molecular weight of 5,000 to 1 million, the end is any of -NH ₂ , -OH, or -NCO which can be sealed at the end. -[(Alternating copolymer 1)-(Alternating copolymer 2)]-Formula (3) Alternating copolymer 1: Polyurea-based alternating copolymer, which is an addition of a diisocyanate compound <A> and a diamine compound <B> A polymerized copolymer comprising a repeating unit represented by formula (1)-[(A)-(B)]-formula (1), a weight average molecular weight of 500 to 300,000, and both ends of which are -NH ₂ or -NCO; Alternating copolymer 2: At least one alternating copolymer selected from polyurea-based alternating copolymer 2-1 and polyurethane-based alternating copolymer 2-2, the polyurea-based alternating copolymer 2-1 is Addition polymerization copolymer of a diisocyanate compound <A> and a diamine compound <C ¹ >, and containing the formula (2-1)-[(A)-(C ¹ )]-Formula (2-1) The repeating unit has a weight average molecular weight of 500 to 300,000, and both ends are -NCO or -NH ₂ ; the polyurethane-based alternating copolymer 2-2 is a diisocyanate compound <A> and a diol compound <C ^2> addition polymerization copolymers, and comprising the formula (2-2) - [(a) - (C 2)] - repeating units of formula (2-2), the weight average molecular weight of 500 to 300,000 Has -NCO or -OH at both ends; (wherein (A) each independently represents at least one kind of aliphatic isocyanate structural unit having a cyclic structure in the molecule; (B) each independently represents a member selected from an aromatic diamine, At least one structural unit among an aromatic diamine having an ether bond and an aliphatic diamine having a cyclic skeleton; (C ¹ ) represents a member selected from the group consisting of a linear aliphatic diamine, an aliphatic diamine having an ether bond, and At least one structural unit in a diamine of a siloxane skeleton; (C ² ) represents at least one selected from a linear aliphatic diol, an aliphatic diol having an ether bond, and a diol having a siloxane skeleton Structural unit: where both ends of the alternating copolymer 1 are -NCO, both ends of the alternating copolymer 2 are -NH ₂ or -OH; and when both ends of the alternating copolymer 1 are -NH ₂ , the alternating copolymer Both ends of -2 are -NCO) [2] The block copolymer according to [1], wherein both ends of the alternating copolymer 1 are -NCO, and both ends of the alternating copolymer 2 are -NH ₂ or- OH. [3] The block copolymer according to [1], wherein both ends of the alternating copolymer 1 are -NH ₂ , and both ends of the alternating copolymer 2 are -NCO. [4] The block copolymer according to any one of [1] to [3], wherein the alternating copolymer 2 is a polyurea-based alternating copolymer 2-1. [5] The block copolymer according to any one of [1] to [3], wherein the alternating copolymer 2 is a polyurethane-based alternating copolymer 2-2. [6] The block copolymer according to any one of [1] to [5], wherein the diisocyanate compound <A> is a compound represented by the following formula (I) to formula (X), In the following formulae (I) to (X), R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen or an alkyl group having 1 to 7 carbon atoms, and X is each independently 1 carbon atom. An alkylene group of ∼7, Y is independently oxygen, sulfur, a linear or branched alkylene group having 1 to 7 carbon atoms, -C (CF ₃ ) ₂ -or -SO _2- . [7] A resin composition comprising: the block copolymer according to any one of [1] to [6]; and a solvent in which the block copolymer is dissolved. [8] The resin composition according to [7], wherein the solvent comprises propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, 4-methyl-2-pentanone, N, N-dimethylpropanidine At least one of an amine, tetramethylurea, and dimethylsulfine. [9] A coating film comprising a solid component obtained by removing the solvent from the resin composition according to [7] or [8]. [10] A resin film formed of a solid component obtained by removing the solvent from the resin composition according to [7] or [8]. [11] A resin film including at least two layers of a resin film formed from a solid component obtained by removing the solvent from the resin composition according to [7] or [8]. [12] A resin film comprising: a resin film (H), which is a resin film (H) formed from a solid component obtained by removing the solvent from the resin composition according to [7] or [8] And the block copolymer is the block copolymer according to [4]; and the resin film (S) is obtained by removing the solvent from the resin composition according to [7] or [8], and The obtained solid film is a resin film (S), and the block copolymer is the block copolymer according to [5]. [13] The resin film according to [12], comprising three layers laminated in the order of the resin film (H) / the resin film (S) / the resin film (H). [14] The resin film according to [12], comprising three layers laminated in the order of the resin film (S) / the resin film (H) / the resin film (S). [15] An Organic Light-Emitting Diode (OLED) element, comprising: the resin film according to any one of [10] to [14]. [16] A light emitting device including the OLED element according to [15]. [Effect of the invention]

The block copolymer obtained in the present invention exhibits the following effects: it is soluble in general organic solvents, and has excellent transparency, heat resistance, film-forming properties, and flexibility.

This application is based on Japanese Patent Application No. 2017-174735 filed in Japan on September 12, 2017 and Japanese Patent Application No. 2018-151547 filed on August 10, 2018, and its content is based on Part of the content of the application. The present invention can be more fully understood from the following detailed description. The further application range of this invention will become clear by the following detailed description. However, the detailed description and specific examples are ideal embodiments of the present invention, and are described for illustrative purposes only. The reason is that, based on this detailed description, those skilled in the art will understand various changes and modifications within the spirit and scope of the present invention. The applicant does not intend to present any of the recorded embodiments to the public, and those who change or replace the statements in the case that may not be included in the scope of the patent application are also made part of the invention under the equality theory.

Hereinafter, the block copolymer of this invention, the manufacturing method of a block copolymer, and these uses are demonstrated in detail. However, the present invention is not limited to the following embodiments.

The block copolymer of the present invention is a block copolymer which is an addition polymerization copolymer of the following alternating copolymer 1 and the following alternating copolymer 2 and includes a repeating unit represented by formula (3), and weighs The average molecular weight is 50 to 1 million, and the end is any of -NH ₂ , -OH, or -NCO which can be sealed at the end. -[(Alternating copolymer 1)-(Alternating copolymer 2)]-Formula (3) Where both ends of alternating copolymer 1 are -NCO, both ends of alternating copolymer 2 are -NH ₂ or -OH ; When both ends of the alternating copolymer 1 are -NH ₂ , both ends of the alternating copolymer 2 are -NCO. Hereinafter, the elements constituting the block copolymer will be described in order.

1 Alternating copolymer 1 Alternating copolymer 1 is a polyurea-based alternating copolymer, which is an addition polymerization copolymer of a diisocyanate compound <A> and a diamine compound <B>, and contains formulae (1)-[(A) -(B)]-The repeating unit represented by formula (1) has a weight average molecular weight of 500 to 300,000, and both ends are -NH ₂ or -NCO. (Wherein (A) is at least one kind of aliphatic diisocyanate structural unit having a cyclic structure in the molecule, and (B) is each independently selected from an aromatic diamine, an aromatic diamine having an ether bond, and a cyclic At least one of the structural units of the aliphatic diamine of the skeleton)

The alternating copolymer 1 is obtained by addition polymerization of a diisocyanate compound <A> and a diamine compound <B>. The diisocyanate compound <A> and the diamine compound <B> correspond to the structural unit (A) and the structural unit (B) in the alternating copolymer 1, respectively. The bonding site between the structural unit (A) and the structural unit (B) becomes a urea structure (-NH-CO-NH-).

The structural unit of the alternating copolymer 1 is considered to be a structural unit (hard segment) which contributes to rigidity and heat resistance in the physical properties of the block copolymer.

1.1 Diisocyanate compound <A> The diisocyanate compound <A> which can be used in the present invention is not particularly limited as long as it is an aliphatic diisocyanate compound having a cyclic structure in the molecule, and specific examples thereof include the following formulas (I) to the diisocyanate compound represented by the formula (X). In the following formulae (I) to (X), R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen or an alkyl group having 1 to 7 carbon atoms, and X is each independently 1 to 6 carbon atoms. The alkylene group of 7 and Y are each independently oxygen, sulfur, a linear or branched alkylene group having 1 to 7 carbon atoms, -C (CF ₃ ) ₂ -or -SO _2- .

In addition, the so-called aliphatic diisocyanate of the present invention is a compound having two isocyanate groups in the molecule in which an isocyanate group is directly bonded to the carbon of a linear or branched aliphatic hydrocarbon or an aliphatic ring.

In the specific example, the diisocyanate compound represented by the formula (V), the formula (VI), or the formula (VIII) has high solubility in a solvent, and is therefore preferred. Furthermore, when high transparency or heat resistance is required, the diisocyanate compound represented by Formula (V) and Formula (VI) can be used especially suitably.

Furthermore, the diisocyanate compound <A> which can be used in the present invention is not particularly limited as long as it is an aliphatic diisocyanate compound having a cyclic structure in the molecule, and examples thereof include those disclosed in Japanese Patent Laid-Open No. 2016-199694 Compound.

Aliphatic diisocyanate with a cyclic structure in the molecule: isophorone diisocyanate, (bicyclic [2.2.1] heptane-2,5-diyl) bismethylene diisocyanate, (bicyclic [2.2.1] Heptane-2,6-diyl) bismethylene diisocyanate, 2β, 5α-bis (isocyanate) norbornane, 2β, 5β-bis (isocyanate) norbornane, 2β, 6α-bis (isocyanate) Borne, 2β, 6β-bis (isocyanate) norbornane, 2,6-bis (isocyanate methyl) furan, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) ) Cyclohexane, dicyclohexylmethane diisocyanate, 4,4-isopropylidene bis (cyclohexyl isocyanate), cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate , 2,2'-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanate-n-butylene) pentaerythritol, dimer acid diisocyanate, 3,8-bis (isocyanate methyl) tricyclodecane, 3,9-bis (isocyanatemethyl) tricyclodecane, 4,8-bis (isocyanatemethyl) tricyclodecane, 4,9-bis (isocyanatemethyl) tricyclodecane, 1,5-di Isocyanate decalin, 2,7- Isocyanate decalin, 1,4-decalin diisocyanate, 2,6-diisocyanate decalin, dicyclohexyl sulfide-4,4'-diisocyanate, octane-thia-tricyclo diisocyanate

The diisocyanate compound described above may be used alone, or two or more thereof may be used in combination.

1.2 Diamine compound <B> The diamine compound <B> which can be used in the present invention is independently selected from the group consisting of an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton. The diamine compound in is not particularly limited. For example, a diamine compound disclosed in Japanese Patent Laid-Open No. 2014-65921 can be used.

In addition, the "aliphatic diamine having a cyclic skeleton" is a linear or branched aliphatic hydrocarbon having an amine group directly bonded to it, a cyclic structure in the molecule, and two amine groups in the molecule. compound of. The "aromatic diamine" is a compound having an amine group directly bonded to the carbon of the aromatic ring and having two amine groups in the molecule.

In particular, the diamine compound <B> which can be used to impart high heat resistance is a diamine compound selected from the group consisting of an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton. Examples include: 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-di Amino diphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 2 , 2'-diaminodiphenylpropane, benzidine, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-Aminophenoxy) phenyl] -4-methylcyclohexane, bis [4- (4-aminobenzyl) phenyl] methane, 1,1-bis [4- (4-amine Benzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] 4-methylcyclohexane , 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] -4-methylcyclohexyl Alkanes, 1,1-bis [4- (4-aminobenzyl) phenyl] methane, 4,4'-bis (4-aminophenoxy) biphenyl, 1,6-bis (4- ( (4-aminophenyl) methyl) phenyl) hexane, α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, 1,4-diamino ring Hexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4'-diaminodicyclohexylmethane, and the like.

In the specific examples, in terms of heat resistance or mechanical properties, 4,4'-diaminodiphenylmethane, 1,3-bis (4-aminophenoxy) benzene, and 2,2- Bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (aminomethyl) cyclohexane, 4,4'-diaminodicyclohexylmethane, particularly preferably 4,4'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane was used.

In particular, as the diamine compound <B> that can be used to impart high heat resistance, for example, an aliphatic diamine having a cyclic skeleton represented by the formula (XIII-1) and the formula (XIII-2) can be mentioned.

For example, the aliphatic diamine which has a cyclic skeleton represented by Formula (XIV-1)-Formula (XIV-3) is mentioned.

Examples thereof include aromatic diamines represented by the formulae (XV-1) to (XV-5).

Examples include the aromatic diamines represented by the formulae (XVI-1) to (XVI-12), (XVI-20) to (XVI-30), and (XVI-13) to (XVI- 19) An aromatic diamine having an ether bond as shown in FIG.

Examples include aromatic diamines represented by the formulae (XVII-1) to (XVII-4), and aromatic diamines having an ether bond represented by the formulae (XVII-5) and (XVII-6).

Examples include aromatic diamines represented by the formulae (XVIII-1) to (XVIII-7), and aromatic diamines having an ether bond represented by the formulae (XVIII-8) to (XVIII-11).

The diamine compound <B> of the present invention is not limited to the diamine of the present specification, and other various forms of diamine can be used within the scope of achieving the object of the present invention. The diamine compounds described above may be used alone or in combination of two or more.

2 Alternating copolymer 2 Alternating copolymer 2 is at least one alternating copolymer selected from polyurea-based alternating copolymer 2-1 and polyurethane-based alternating copolymer 2-2, and the polyurea-based alternating copolymerization The object 2-1 is an addition polymerization copolymer of a diisocyanate compound <A> and a diamine compound <C ¹ >, and includes the formula (2-1)-[(A)-(C ¹ )]-formula (2- 1) The repeating unit shown has a weight average molecular weight of 500 to 300,000 and both ends are -NCO or -NH ₂ ; the polyurethane-based alternating copolymer 2-2 is a diisocyanate compound <A> and An addition polymerization copolymer of a diol compound <C ² >, which contains a repeating unit represented by formula (2-2)-[(A)-(C ² )]-formula (2-2), and has a weight average molecular weight of 500,000 to 300,000, with -NCO or -OH at both ends. (Wherein (A) each independently represents at least one kind of aliphatic isocyanate structural unit having a cyclic structure in the molecule; (C ¹ ) represents a member selected from a linear aliphatic diamine, an aliphatic diamine having an ether bond, and At least one structural unit in a diamine having a siloxane skeleton; (C ² ) represents at least one selected from a linear aliphatic diol, an aliphatic diol having an ether bond, and a diol having a siloxane skeleton. A structural unit)

As the alternating copolymer 2, a polyurea-based alternating copolymer 2-1 represented by the formula (2-1) and a polyurethane-based alternating copolymer 2-2 represented by the formula (2-2) can be used. Either of them can be used in combination.

The alternating copolymer 2 is obtained by addition polymerization of a diisocyanate compound <A> and a diamine compound <C ¹ > or a diol compound <C ² >. <A> diisocyanate compound, a diamine compound <C ^1> and the diol compound <C ^2>, respectively, corresponding to an alternating copolymer the structural units (A) 2, structural units (C ¹⁾ and the structural units (C ²⁾ . The bonding site between the structural unit (A) and the structural unit (C ¹ ) becomes the urea structure (-NH-CO-NH-), and the bonding site between the structural unit (A) and the structural unit (C ² ) becomes urethane. Ester structure (-NH-CO-O-).

The structural unit of the alternating copolymer 2 is considered to be a structural unit (soft segment) which contributes to solubility, softness, and elongation in the physical properties of the block copolymer.

2.1 Diisocyanate compound <A> The diisocyanate compound <A> which can be used in the alternating copolymer 2 is the same as the diisocyanate compound <A> used in the alternating copolymer 1.

2.2 Diamine compound <C ¹ > and diol compound <C ² > The diamine compound <C ¹ > or the diol compound <C ² > used in the alternating copolymer 2 may be selected from any of these. The polyurea-based alternating copolymer 2-1 and the polyurethane-based alternating copolymer 2-2 can be obtained by addition polymerization of each with the diisocyanate compound <A>. In addition, a diamine compound <C ¹ > and a diol compound <C ² > may be used in combination. In this case, the alternating copolymer 2 becomes a copolymer including both a urea structure and a urethane structure.

2.2.1 Diamine compound <C ¹ > The diamine compound <C ¹ > is selected from the group consisting of a linear aliphatic diamine compound, an aliphatic diamine compound having an ether bond, and a diamine compound having a siloxane skeleton. At least one. For example, compounds disclosed in Japanese Patent Laid-Open No. 2014-65921 can be used.

The "aliphatic diamine" according to the present invention is a straight-chain, branched aliphatic hydrocarbon or an aliphatic ring having an amine group directly bonded to the carbon and having two amine groups in the molecule.

In particular, the diamine compound <C ¹ > which can be used to impart high transparency is a diamine compound selected from the group consisting of a linear aliphatic diamine, an aliphatic diamine having an ether bond, and a diamine having a siloxane skeleton, Specific examples thereof include 1,4-diaminobutane, 1,6-diaminohexane, 1,12-diaminododecane, and 1,2-bis (2-aminoethyl). (Oxy) ethane, diethylene glycol bis (3-aminopropyl) ether, 1,4-butanediol bis (3-aminopropyl) ether, 1,3-bis (3-aminopropyl) Group) -tetramethyldisilazane, a diamine compound having a siloxane skeleton represented by the following formula (XI), and the like.

In the formula, R ₅ and R _{6 are} independently an alkyl group or a phenyl group having 1 to 3 carbon atoms, and R _{7 is} independently a methylene group, a phenylene group, or an phenylene group having at least one hydrogen substituted by an alkyl group. x is independently an integer of 1 to 6, and y is an integer of 0 to 70.

In the specific examples, in terms of transparency or mechanical properties, 1,12-diaminododecane, diethylene glycol bis (3-aminopropyl) ether, and silicon having formula (XI) As the diamine compound having an oxane skeleton, diethylene glycol bis (3-aminopropyl) ether and a diamine compound having a siloxane skeleton of formula (XI) can be preferably used.

In particular, as the diamine compound <C ¹ > which can be used to impart high transparency, linear aliphatic diamines represented by formula (XII-1) to formula (XII-3), and formula (XII- 4) The aliphatic diamine having an ether bond represented by the formula (XII-8). In the formula (XII-7), n is an integer of 1 to 30. In the formula (XII-8), a is 0 to 20, b is 0 to 70, and c is 1 to 90.

As the aliphatic diamine having an ether bond represented by the formula (XII-8), for example, Mitsui Fine Chemical Co., Ltd. trade name: Jeffamine D-230 (a = 0, b = 0, c = 2 ～ 3), D-400 (a = 0, b = 0, c = 5 ～ 6), D-2000 (a = 0, b = 0, c = about 33) , D-4000 and other Jeffamine D series; Jeffamine ED-600 (b = 9.0, a + c = 3.6), ED-900 (b = 12.0, a + c = 3.6), ED-2003 (b = 38.7, a + c = 6.0) and other Jeffamine ED series; etc.

2.2.2 Diol compound <C ² > Diol compound <C ² > is at least one selected from the group consisting of a linear aliphatic diol, an aliphatic diol having an ether bond, and a diol having a siloxane skeleton. As the diol compound <C ² >, a compound having a structure in which two -NH ₂ in the diamine compound <C ¹ > are substituted with -OH can be used.

Specific examples of the diol compound <C ² > are listed below, but are not limited to these examples. Examples of the alkylene glycol compound or polyoxyalkylene glycol compound include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,3-propylene glycol, dipropylene glycol, Tripropylene glycol, tetramethylene glycol, polybutylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,7-heptanediol, 1,6-hexanediol, hexanediol, neopentyl glycol, poly1,2-butanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, methylpentanediol modified polybutylene glycol, propylene glycol modified polybutylene glycol, ethyl acetate Glycol-propylene glycol · block copolymer, ethylene glycol-butylene glycol copolymer, 2-methyl-1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5 -Pentylene glycol, Silaplane FM4401 (both terminal modified silicon compounds manufactured by JNC), Silaplane FM4411 (both terminal modified silicon compounds manufactured by JNC) Compound, Mn = 1000), Silaplane FM4421 (both terminal modified silicon compounds manufactured by JNC), Mn = 500 0), Silaplane FM4425 (both terminal modified silicon compounds manufactured by JNC (stock), Mn = 10000). These compounds can be used alone or in combination of two or more.

3 Block copolymer The block copolymer of the present invention is a block copolymer which is an addition polymerization copolymer of the alternating copolymer 1 and the alternating copolymer 2 and includes a repetition represented by formula (3) The unit has a weight average molecular weight of 50 to 1 million, and the end is any of -NH ₂ , -OH, or -NCO which can be sealed at the end. -[(Alternating copolymer 1)-(Alternating copolymer 2)]-Formula (3) The alternating copolymer 1 and the alternating copolymer 2 are bonded via a urea bond or a urethane bond.

Regarding the block copolymer of the present invention, when both ends of the alternating copolymer 1 are -NCO, both ends of the alternating copolymer 2 are -NH ₂ or -OH; when both ends of the alternating copolymer 1 are -NH ₂ Both ends of the alternating copolymer 2 are -NCO. These two terminal groups undergo an addition polymerization reaction to form a urea bond or a urethane bond, thereby becoming a block copolymer of the present invention.

4 Method for Producing Block Copolymer Hereinafter, the method for producing the block copolymer of the present invention will be collectively described based on the stages of producing the alternating copolymer 1 and the alternating copolymer 2.

In the addition polymerization reaction or the polycondensation reaction, the charging ratio (molar ratio) of two monomers is changed, whereby both an alternating copolymer having a terminal group corresponding to the monomer structure and a The molecular weight is arbitrarily controlled. This situation is documented in Billmeyer. FW; Step-Reaction (Condensation) Polymerization. In Textbook of Polymer Science; John Wiley & Sons (John Wiley &Sons); Singapore (Singapore), 1994; pp35-39.

Based on the above theory, when both ends of the alternating copolymer 1 constituting the block copolymer are set to -NCO, both ends of the alternating copolymer 2 need to be set to -NH ₂ or -OH, and vice versa, In the case where both ends of the alternating copolymer 1 are -NH ₂ , both ends of the alternating copolymer 2 need to be -NCO.

For example, in the case where both ends of the alternating copolymer 1 are -NCO, in the step (step 1) of addition-polymerizing the diisocyanate compound <A> and the diamine compound <B>, as long as it is relative to the diamine The mole number of the compound <B> may be a larger number than the mole number of the diisocyanate compound <A>. For example, when the molar number of the diisocyanate compound <A> is set to n1, and the molar number of the diamine compound <B> is set to n2, the relationship is preferably 1.06 ≦ n1 / n2 ≦ 1.9 The respective mole numbers are adjusted. In this manner, the weight average molecular weight of the alternating copolymer 1 having -NCO at both ends can be adjusted to a range of 500 to 300,000.

In this case, since the both ends of the alternating copolymer 2 are -NH ₂ or -OH, the diisocyanate compound <A> and the diamine compound <C ¹ > or the diol compound <C ² > are polymerized. In the step (step 2), the Molar number of the diamine compound <C ¹ > or the diol compound <C ² > may be used more than the Molar number of the diisocyanate compound <A>. For example, when the mole number of the diisocyanate compound <A> is set to n1 and the mole number of the diamine compound <C ¹ > or the diol compound <C ² > is set to n2, 1.06 ≦ n2 /n1≦1.9, the respective mole numbers are adjusted. In this manner, the weight average molecular weight of the alternating copolymer 2 having -NH ₂ at both ends can be adjusted to a range of 500 to 300,000.

In addition, for example, in the case where both ends of the alternating copolymer 1 are -NH ₂ , in the step (step 1) of addition-polymerizing the diisocyanate compound <A> and the diamine compound <B>, the relative The Molar number of the diamine compound <B> may be used more for the Molar number of the diisocyanate compound <A>. For example, when the molar number of the diisocyanate compound <A> is set to n1 and the molar number of the diamine compound <B> is set to n2, the relationship is preferably 1.06 ≦ n2 / n1 ≦ 1.9 The respective mole numbers are adjusted. In this manner, the weight average molecular weight of the alternating copolymer 1 having both ends of -NH ₂ can be adjusted to a range of 500 to 300,000.

In this case, since both ends of the alternating copolymer 2 are -NCO, a step of polymerizing the diisocyanate compound <A> and the diamine compound <C ¹ > or the diol compound <C ² > (Step 2) ), The mole number of the diisocyanate compound <A> may be used more than the mole number of the diamine compound <C ¹ > or the diol compound <C ² >. For example, preferably the number of moles of diisocyanate compound <A> set n1, a diamine compound <C ^1> or diol compound <C ^2> is set to the number of moles of n2, so as to be 1.06 ≦ n1 /n2≦1.9, the respective mole numbers are adjusted. In this manner, the weight average molecular weight of the alternating copolymer 2 whose both ends are -NCO can be adjusted in the range of 500 to 300,000.

Next, a method for producing a block copolymer will be described. The block copolymer uses (i) a method for producing the block copolymer by introducing the alternating copolymer 1 obtained in step 1 and the alternating copolymer 2 obtained in step 2 into the same reaction vessel and performing an addition polymerization reaction. (Ii) A method for producing a block copolymer by introducing the alternating copolymer 1 obtained in step 1 into a reaction vessel, and thereafter performing step 2 (iii) introducing the alternating copolymer 2 obtained in step 2 into a reaction In the container, step 1 is then performed to produce the block copolymer method (iv) After performing step 1 in the same container, step 2 is continued to perform the method (v) to produce the block copolymer in the same container. After step 2 is performed within step, step 1 is continued, and the stepwise manufacturing method exemplified by the method for manufacturing a block copolymer (hereinafter, the step polymerization method) is performed. The block copolymer can be obtained in any one of the stage polymerization methods. In order to obtain the desired characteristics, more than one stage polymerization method can be combined, and the selected stage polymerization method can be repeatedly performed multiple times.

Next, a structural change of the block copolymer will be described. In Step 1 and Step 2, since the molecular weights of the alternating copolymer 1 and the alternating copolymer 2 can be arbitrarily controlled, block copolymers having different block chain lengths can be obtained. It is also possible to control the molecular weight of the block copolymer by changing the molar ratios of the alternating copolymer 1 and the alternating copolymer 2 obtained in step 1 and step 2. The weight average molecular weight of the block copolymer is preferably in the range of 5,000 to 1 million, and more preferably 5,000 to 300,000.

5 Other diisocyanate compounds <D> In the block copolymer of the present invention, the alternating copolymer 1 and the alternating copolymer 2 each have a structural unit of a diisocyanate compound <A>, that is, an aliphatic isocyanate structural unit having a cyclic structure ( A), but another diisocyanate compound <D> may be used instead of a part of the diisocyanate compound <A> (structural unit (D)). Other diisocyanate compounds may be included in a part of the alternating copolymer 1 or a part of the alternating copolymer 2, and may be sandwiched in the structure of the portion to which each alternating copolymer is bonded, or may be bonded to Block copolymer ends.

The other diisocyanate compound is not particularly limited as long as it is a compound other than the diisocyanate compound <A> and having two diisocyanate groups in the molecule. As specific examples of other diisocyanate compounds, the compounds shown below can be used.

Preferred examples of other diisocyanate compounds include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, and 3-methyl-pentane. Alkane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, 2,4'-tolylene diisocyanate (2,4'-tolylene diisocyanate, 2,4'-TDI ), 2,6'-tolylene diisocyanate (2,6'-tolylene diisocyanate, 2,6'-TDI), 4,4'-diphenylmethane diisocyanate (MDI), Xylylene diisocyanate, 1,5-naphthalene diisocyanate, etc.

Furthermore, examples of other diisocyanate compounds include aliphatic diisocyanates, aromatic diisocyanates, sulfur-containing aliphatic diisocyanates, aliphatic thioether-based diisocyanates, and aromatics disclosed in Japanese Patent Laid-Open No. 2016-199694. Group thioether-based diisocyanates, aliphatic fluorene-based diisocyanates, aromatic fluorene-based diisocyanates, sulfonate-based diisocyanates, aromatic sulfonamide-based diisocyanates, sulfur-containing heterocyclic diisocyanates, and the like. Specific examples of these as the diisocyanate compound include the following compounds.

In addition, the so-called aromatic diisocyanate referred to in the present invention is a compound having two isocyanate groups in the molecule in which an isocyanate group is directly bonded to a carbon of an aromatic ring. The so-called heterocyclic diisocyanate of the present invention is a compound having two isocyanate groups in the molecule, in which an isocyanate group is directly bonded to a carbon of a heterocyclic ring containing a hetero atom.

Furthermore, the so-called thioether-based diisocyanate, fluorene-based diisocyanate, sulfonate-based diisocyanate, and sulfonamide-based diisocyanate of the present invention are sulfide, sulfonium, sulfonate, and sulfonamide in the molecule, respectively. Structure and a compound having two isocyanate groups in the molecule.

Aliphatic diisocyanates: ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'- Dimethylpentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate , 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-trimethylundemethylene diisocyanate, 1,3,6-trimethylhexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane, bis (isocyanateethyl) carbonate, bis (Isocyanate ethyl) ether, 1,4-butanediol dipropyl ether ω, ω'-diisocyanate, lysine diisocyanate methyl ester

Aromatic diisocyanates: xylylene diisocyanate (ortho, m, p), tetrachloro-m-xylylene diisocyanate, 4-chloro-m-xylylene diisocyanate, 4,5-dichloro-m- Xylylene diisocyanate, 2,3,5,6-tetrabromo-p-xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, 4-ethyl-m-xylylene diisocyanate Isocyanate, bis (isocyanateethyl) benzene, bis (isocyanatepropyl) benzene, 1,3-bis (α, α-dimethylisocyanatemethyl) benzene, 1,4-bis (α, α-dimethyl) Isocyanate methyl) benzene, α, α, α ', α'-tetramethylxylylene diisocyanate, bis (isocyanatebutyl) benzene, bis (isocyanatemethyl) naphthalene, bis (isocyanatemethyl) diphenyl Ether, bis (isocyanate ethyl) phthalate, 2,6-bis (isocyanate methyl) furan, phenylene diisocyanate, toluene diisocyanate, ethyl phenylene diisocyanate, isopropyl phenylene Diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, naphthalene diisocyanate, methylnaphthalene diisocyanate, Diisocyanate, tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4 , 4'-diisocyanate, bis (isocyanatephenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, phenyl isocyanate methyl isocyanate, phenyl isocyanate ethyl isocyanate, tetra Hydronaphthalene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propanediol diphenyl Ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofuran diisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate

Sulfur-containing aliphatic diisocyanates: thiodiethyldiisocyanate, thiodipropyldiisocyanate, thiodihexyldiisocyanate, dimethylfluorene diisocyanate, dithiodimethyldiisocyanate, dithiodiisocyanate Ethyl diisocyanate, 1,2-bis (2-isocyanate ethylthio) ethane, 2,4-dithiapentane-1,3-diisocyanate, 2,4,6-trithiaheptane -3,5-diisocyanate, 2,4,7,9-tetrathiapentane-5,6-diisocyanate, bis (isocyanate methylthio) phenylmethane, bis (isocyanate methylthio) methane , Bis (isocyanate ethylthio) methane, bis (isocyanate ethylthio) ethane, bis (isocyanate methylthio) ethane, 1,5-isocyanate 2-isocyanate methyl-3-thiopentane

Aliphatic sulfide-based diisocyanates: bis [2- (isocyanatemethylthio) ethyl] sulfide, bis (isocyanatemethyl) sulfide, bis (isocyanateethyl) sulfide, bis (isocyanatepropyl) sulfide Ether, bis (isocyanatehexyl) sulfide, bis (isocyanate methyl) disulfide, bis (isocyanate ethyl) disulfide, bis (isocyanatepropyl) disulfide

Aromatic sulfide-based diisocyanates: diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4 ' -Diisocyanate dibenzyl sulfide, bis (4-isocyanate methylbenzene) sulfide, 4,4'-methoxybenzene thioglycol-3,3'-diisocyanate, diphenyl disulfide -4,4'-diisocyanate, 2,2'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl disulfide-5,5 '-Diisocyanate, 3,3'-dimethyldiphenyl disulfide-6,6'-diisocyanate, 4,4'-dimethyldiphenyl disulfide-5,5'-diisocyanate , 3,3'-dimethoxydiphenyldisulfide-4,4'-diisocyanate, 4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate

Aliphatic fluorene-based diisocyanate: bis (isocyanate methyl) fluorene

Aromatic fluorene-based diisocyanates: diphenylfluorene-4,4'-diisocyanate, diphenylfluorene-3,3'-diisocyanate, benzylidenefluorene-4,4'-diisocyanate, diphenylmethane碸 -4,4'-diisocyanate, 4-methyldiphenylmethane 碸 -2,4'-diisocyanate, 4,4'-dimethoxydiphenylfluorene-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzylfluorene, 4,4'-dimethyldiphenylfluorene-3,3'-diisocyanate, 4,4'-di- Tert-butyldiphenylfluorene-3,3'-diisocyanate, 4,4'-dimethoxyphenethylidene-3,3'-diisocyanate, 4,4'-dichlorodiphenyl Hydrazone-3,3'-diisocyanate

Sulfonate-based diisocyanates: 4-methyl-3-isocyanate benzenesulfonyl-4'-isocyanate phenol ester, 4-methoxy-3-isocyanate benzenesulfonyl-4'-isocyanate phenol ester

Aromatic sulfonamido-based diisocyanates: 4-methyl-3-isocyanate, benzenesulfonamidoanilide (anilide) -3'-methyl-4'-isocyanate, diphenylsulfonamido-ethylenediamine-4, 4'-diisocyanate, 4,4'-dimethoxybenzenesulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3-isocyanate -3'-isocyanate

Sulfur-containing heterocyclic diisocyanates: thiophene-2,5-diisocyanate, thiophene-2,5-diisocyanate methyl, 1,4-dithiane-2,5-diisocyanate, 1,4-diisocyanate Thiane-2,5-diisocyanate methyl, 1,3-dithiolane-4,5-diisocyanate, 1,3-dithiocyclopentane-4,5-diisocyanate Methyl, 1,3-dithiacyclopentane-2-methyl-4,5-diisocyanate methyl, 1,3-dithiacyclopentane-2,2-diisocyanate ethyl, tetrahydro Thiophene-2,5-diisocyanate, tetrahydrothiophene-2,5-diisocyanate methyl, tetrahydrothiophene-2,5-diisocyanate ethyl, tetrahydrothiophene-3,4-diisocyanate methyl, 2- (1,1-diisocyanate methyl) thiophene, 3- (1,1-diisocyanate methyl) thiophene, 2- (2-thienylthio) -1,2-diisocyanate propane, 2- (3- (Thienylthio) -1,2-diisocyanate propane, 3- (2-thienyl) -1,5-diisocyanate-2,4-dithiopentane, 3- (3-thienyl) -1 2,5-diisocyanate-2,4-dithiopentane, 3- (2-thienylthio) -1,5-diisocyanate-2,4-dithiopentane, 3- (3-thiophene Thio) -1,5-diisocyanate-2,4-dithiopentane, 3- (2-thiophene) (Thiomethyl) -1,5-diisocyanate-2,4-dithiopentane, 3- (3-thienylthiomethyl) -1,5-diisocyanate-2,4-dithia Pentane, 2,5- (diisocyanate methyl) thiophene, 2,3- (diisocyanate methyl) thiophene, 2,4- (diisocyanate methyl) thiophene, 3,4- (diisocyanate methyl) thiophene , 2,5- (diisocyanate methylthio) thiophene, 2,3- (diisocyanate methylthio) thiophene, 2,4- (diisocyanate methylthio) thiophene, 3,4- (diisocyanate (Methylthio) thiophene, 2,4-bisisocyanate methyl-1,3,5-trithiane

In addition, diisocyanate compounds are commonly used in the production of polyureas or polyurethanes, but in the industry, the corresponding diamines are used as starting materials and reacted with phosgene. While manufacturing. That is, the desired diisocyanate compound <A> or other diisocyanate compounds can be produced using the diamine compound <B> as a starting material.

6 Terminals of Block Copolymer The terminal group of the block copolymer of the present invention is basically any one of -NH ₂ , -OH, or -NCO, and these terminal groups may be sealed. By sealing the ends, the storage stability of the block copolymer can be improved. In order to seal the terminal group, the terminal sealant exemplified below can be used.

When the terminal group is -NCO, a compound having a -NH ₂ group, a -OH group, a -COOH group, and a -SO ₂ H group can be used as the terminal sealant.

Specific examples of the compound having an -NH ₂ group that can be used as a terminal sealant include 1-aminobutane, 4-ethynylaniline, 3-ethynylaniline, propargylamine, and 3-amino group. Butyne, 4-aminobutyne, 5-aminopentyne, 4-aminopentyne, allylamine, 7-aminoheptyne, m-aminostyrene, p-aminostyrene, m-amine -Α-methylstyrene, 3-aminophenylacetylene, 4-aminophenylacetylene. Among these, 1-aminobutane is preferable at the point which is excellent in reactivity. These monoamine compounds may be used singly or in combination of two or more kinds.

Specific examples of the compound having an -OH group which can be used as a terminal sealant include a monoalcohol compound having 1 to 18 carbon atoms. Examples of the monoalcohol compound having 1 to 18 carbon atoms include linear monoalcohols (methanol, ethanol, n-propanol, n-butanol, pentanol, hexanol, octanol, nonanol, decanol, undecanol, Dodecanol, tridecanol, tetradecanol, cetyl alcohol, stearyl alcohol, etc.); monoalcohols with branched chains (isopropanol, second butanol, isobutanol or third butanol, neopentyl alcohol) , 3-methyl-pentanol, 2-ethylhexanol, etc.); monoalcohols having cyclic groups of 6 to 10 carbons [alicyclic group-containing monoalcohols (cyclohexanol, etc.) and aromatic ring-containing Monoalcohols (benzyl alcohol, etc.), etc.]. Further, as specific examples of the compound having an -OH group, a polymer monoalcohol (polyester monoalcohol, polyether monoalcohol, polyether ester monoalcohol, etc.), a cellosolve, and carbitols may be mentioned. Among these, a linear monoalcohol is preferable. Specific examples include methanol, ethanol, n-propanol, and n-butanol. These monoalcohol compounds may be used singly or in combination of two or more kinds.

When a compound having an -OH group is used as the terminal sealant, a general urethane-forming catalyst such as dibutyltin dilaurate can be used as the reaction catalyst. Examples of the urethane catalyst include various nitrogen-containing compounds such as N, N-dimethylaminoethyl ether, triethylamine, triethylenediamine, or N-methylmorpholine. Various metal salts such as potassium acetate, zinc stearate, or tin octoate; various organometallic compounds such as dibutyltin dilaurate; chelate compounds such as zirconyl tetraacetamidate; and the like.

When the terminal reactive group is -NH ₂ or -OH, a compound having a -NCO group can be used as the terminal sealant.

Specific examples of the compound having a -NCO group that can be used as a terminal sealant include phenyl isocyanate, toluene isocyanate, dimethyl isocyanate, cyclohexyl isocyanate, Butyl isocyanate, naphthalate isocyanate, etc. These monoisocyanate compounds may be used alone or in combination of two or more.

When a compound having a -NCO group is used as the terminal sealant, a general urethane-forming catalyst such as dibutyltin dilaurate can be used as the reaction catalyst. Examples of the urethane catalyst include various nitrogen-containing compounds such as N, N-dimethylaminoethyl ether, triethylamine, triethylenediamine, or N-methylmorpholine. Various metal salts such as potassium acetate, zinc stearate, or tin octoate; various organometallic compounds such as dibutyltin dilaurate; chelate compounds such as zirconyl tetraacetamidate; and the like.

7 Reaction solvent The solvent used in the production of the alternating copolymer 1, the alternating copolymer 2, and further the block copolymer of the present invention is not particularly limited as long as it can synthesize these copolymers. Examples of the reaction solvent include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane Ethane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate Ester, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, Propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether (1-methoxy-2-propanol), Triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, butylene glycol monoethyl ether Ether, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1- (2 -Hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetamido-2-pyrrolidone, N, N-dimethylformamidine Amine, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropanamide, N-methyl -ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, 4-methyl-2-pentanone, methyl ethyl ketone, acetone, toluene, tetrahydrofuran, Ethyl lactate, 3-methoxy N, N-dimethylpropanamide, isopropanol, n-butanol, n-propanol, N, N-dimethylpropanamide, tetramethylurea, and Methyl sulfene.

Among these, if propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diamine Ethylformamide, N, N-dimethylacetamide, 4-methyl-2-pentanone, N, N-dimethylpropanamide, tetramethylurea, dimethylmethylene, then The polyurea-based alternating copolymer has good solubility and is uniformly polymerized, so it is preferable. These reaction solvents may be used alone or in combination of two or more. Furthermore, other solvents can be mixed and used in addition to the reaction solvent.

It is preferable to use a reaction solvent of 100 parts by weight or more with respect to 100 parts by weight of the total of the diisocyanate compound <A> and the diamine compound <B>, since the reaction proceeds smoothly. The reaction is preferably performed at 0 ° C to 150 ° C for 0.2 hours to 20 hours.

8 Uses of block copolymers The block copolymers of the present invention can be fully utilized as materials for protecting image display devices from impact in the field of image display devices such as liquid crystal displays and organic EL displays. For example, in a liquid crystal display, it can also be used as a film or coating material provided on the surface or back surface of a cover glass or cover film, or on the surface or back surface of a polarizing plate. In organic EL displays, the development of thinness and lightness due to flexibility has increased, and the need to protect elements from external forces such as impact has become extremely high. Along with this, the block copolymer of the present invention is useful as a back film or a coating material provided on a surface or back surface of a cover glass or a cover film, a surface or back surface of a polarizer, an element body, or a coating material. In addition, it can be fully utilized as a material inside an element such as a filler, a sealing material, a barrier material, a buffer material, and a flattening film.

In the automotive field, it is also useful as a material for protecting the exterior or interior of an automobile from impact. For example, it can also be used as a paint protection film or a coating material for protecting the outer coating from flying stones and the like. Can also effectively utilize the excellent impact absorption of block copolymers, and be used as an interlayer film for laminated glass for automobiles, installed in glazing, rear window, and back mirror ), Sensors or the like.

Polyurea or polyurethane-based materials may also be used as biocompatible materials. It can be made into a dialysis membrane by filtering with spinning such as electrospinning, or it can be expected to be applied to hollow filaments such as the heart and lungs of the population and the coating of drip needles embedded in the body for a long time. ) And other medical devices that require blood adaptability.

In the field of building materials, it can be used as a film or coating material to prevent window glass from scattering, for example, to prevent the window glass of high-rise buildings from breaking, scattering, and falling during earthquakes and earthquakes. It can also prevent window glass for safety purposes. Destruction. It is known that by applying polyurea to structural buildings, such as concrete or block fences, the impact resistance can be enhanced, and it can also be used as a coating to prevent structural buildings from collapsing during terrorist operations or earthquakes and earthquakes. Cloth. The polyurea-based alternating copolymer can also be used in the same applications as the block copolymer.

9 Resin Composition The resin composition of the present invention is a composition including the block copolymer and a solvent in which the block copolymer is dissolved. The solvent used in the resin composition of the present invention is not particularly limited as long as it can dissolve the block copolymer. For example, the reaction solvent used in the production of the block copolymer can be used as it is, but it is also possible to add another solvent and use it as a mixed solvent. In addition, the block copolymer can be separated as a solid component and then dissolved in a desired solvent and used. In addition, as a method of separating the block copolymer, a method may be mentioned in which a solution containing the block copolymer and a reaction solvent is put into a lean solvent such as methanol, ethanol, isopropyl ether, etc. with respect to the block copolymer. The block copolymer is precipitated and separated by filtration, washing, and drying. By performing such an operation, it is possible to remove the catalyst used in the production of the block copolymer. Particularly preferred solvents include propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, 4-methyl-2-pentanone, N, N-dimethylpropanamide, tetramethylurea, dimethylimide Alas. These solvents may be used alone or in combination of two or more. When these solvents are used, it is preferable to prevent precipitation of a polymer and produce a transparent and flat film when a film is produced.

The concentration of the block copolymer in the resin composition is not particularly limited. However, in terms of solubility and reactivity, it is preferably 10% by weight to 80% by weight, and more preferably 20% by weight to 50% by weight. The viscosity of the resin composition is preferably adjusted to an appropriate viscosity according to a method for forming a coating film, a thickness of a resin film, and the like. For example, the viscosity of the resin composition of the present invention at 25 ° C may be in the range of 1 mPa · s to 100,000 mPa · s, and it is preferably adjusted to be used in the range of 10 mPa · s to 50,000 mPa · s.

The resin composition of the present invention may further include additives such as an ultraviolet absorber and a light stabilizer (Hindered Amine Light Stabilizer (HALS)).

Examples of the ultraviolet absorber include benzotriazoles, hydroxyphenyltriazines, benzophenones, salicylates, cyanoacrylic acid esters, triazines, or benzophenazyl m-benzenes. Diphenols and so on. These ultraviolet absorbents may be used alone or in combination. It is preferable that the ultraviolet absorber is appropriately selected based on the wavelength of the ultraviolet light to be absorbed, or a combination thereof.

Examples of the ultraviolet absorber include Adekastab LA-46, Adekastab LA-77Y, and Adekastab manufactured by ADEKA Co., Ltd. ) LA-63P, Adekastab LA-72, Adekastab LA-32, TINUVIN 479, TINUVIN manufactured by BASF 292, TINUVIN 123, TINUVIN 384-2, TINUVIN 400 and so on.

The amount of the ultraviolet absorber in the resin composition is not particularly limited. However, in terms of solubility, it is preferably 0.1% to 30% by weight, and more preferably 1% to 15% by weight based on the solid content in the resin composition.

Examples of the light stabilizer (HALS) include TINUVIN (registered trademark) 5100 (general-purpose universal HALS) manufactured by BASF, and TINUVIN 292 (compound name: double (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) decane Diester), TINUVIN 152 (compound name: 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine) -4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine), TINUVIN 144 (compound name: bis (1,2,2,6 , 6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate), TINUVIN 123 (compound name: sebacic acid, reaction product of bis (2,2,6,6-tetramethyl-1- (octyloxy) -4piperidinyl) ester (1, 1-dimethylethyl hydroperoxide and octane)), TINUVIN 111FDL (about 50%, TINUVIN 622, compound name: succinic acid polymer (4- Hydroxy-2,2,6,6-tetramethylpiperidinyl-yl) (in the presence of ethanol); about 50%, chimasso B) 119. Compound name: N-N'-N ''-N '' '-tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperazine) Pyridin-4-yl) amino) triazin-2-yl) -4,7-diazadecane-1,10-diamine), or Adikos manufactured by ADEKA Corporation Adekastab LA series, etc., specifically, LA-52 ((5) -6116), LA-57 ((5) -5555), LA-62 ((5) -5711), LA-67 ( (5) -5755). In addition, the parentheses are the existing chemical substance numbers stipulated by Japan's laws (Chemical Examination Law) related to restrictions on the inspection and production of chemical substances.

The amount of the light stabilizer (HALS) in the resin composition is not particularly limited. However, in terms of solubility, it is preferably 0.1% to 30% by weight, and more preferably 1% to 15% by weight based on the solid content in the resin composition.

In addition, if necessary, active energy ray sensitizers, polymerization inhibitors, waxes, plasticizers, leveling agents, surfactants, dispersants, defoamers, wettability improvers, antistatic agents, and hardening aids can be mixed. Additives, additives that impart antifouling properties or low friction properties, additives that impart damage resistance, heat stabilizers, flame retardants, and release agents, and various other additives.

The resin composition of the present invention is a resin composition capable of forming a resin film having extremely excellent impact absorption. The block copolymer is soluble in general organic solvents and has good heat resistance or mechanical properties. The resin composition of the present invention may be a composition including the polyurea-based alternating copolymer and a solvent in which the polyurea-based alternating copolymer is dissolved.

10 Coating film The coating film of the present invention can be obtained by forming the resin composition of the present invention on a supporting base material or a structure by removing the solvent by applying, printing, casting or the like. The removal method may be, for example, drying, and the drying method is not particularly limited. Examples include heating (hot air) drying, vacuum drying, steam drying, drum drying, spin drying, and suction drying. The drying method or drying conditions may be appropriately selected depending on the type of the solvent of the resin composition, the thickness or shape of the coating film, and the like. For example, in the case of heating and drying, heat treatment using an air-circulating constant temperature oven, a heater using microwaves or far infrared rays, or a heating plate may be mentioned. The drying conditions are not particularly limited as long as the solvent evaporates. For example, the drying temperature may be 40 ° C to 250 ° C, and the drying time may be 1 minute to 24 hours. In addition, heating may be performed in two stages, and if necessary, heating and drying may be performed under a nitrogen atmosphere or under reduced pressure. The shape of the coating film from which the solvent has been removed may be determined according to the use described in the "use of the block copolymer". Alternatively, the solvent may be distilled off after the resin composition is applied to the target portion. With such a structure, a flat coating film is preferable, and thus it is preferable.

11 Resin film The resin film of the present invention is a film obtained by forming a solid component obtained by removing a solvent from the resin composition of the present invention. For example, it can manufacture by the process of coating, drying, and peeling of a resin composition. The resin film may be used in the form of a single layer, or may be repeatedly applied and dried to be used as a film having a plurality of layers. When a plurality of layers are laminated, a combination of resin films having different strengths can further improve impact absorption, and is therefore preferable.

In the case of a single layer, the thickness of the film is preferably 10 μm to 1000 μm, more preferably 20 μm to 500 μm, and even more preferably 30 μm to 400 μm. If it is 30 μm or more, it is easy to obtain it as a film, so it is preferable, and if it is 400 μm or less, it is possible to reduce the thickness of the product, so it is preferable. In the case of two layers, the thickness of each film is preferably at least 1 μm to 999 μm, more preferably 10 μm to 490 μm, and even more preferably 10 μm to 390 μm. If it is 10 μm or more, it is easy to obtain it as a film, so it is preferable, and if it is 390 μm or less, it is possible to reduce the thickness of the product, so it is preferable. In the case of three layers, the thickness of each film is preferably at least 1 μm to 998 μm, more preferably 10 μm to 480 μm, and even more preferably 10 μm to 380 μm. If it is 10 μm or more, it is easy to obtain it as a film, so it is preferable, and if it is 380 μm or less, it is possible to reduce the thickness of the product, so it is preferable. In the case of multiple layers, the total thickness of the resin film is preferably 10 μm to 1000 μm, more preferably 20 μm to 500 μm, and even more preferably 30 μm to 400 μm. If it is 30 μm or more, it is easy to obtain it as a film, so it is preferable, and if it is 400 μm or less, it is possible to reduce the thickness of the product, so it is preferable.

The formation of the resin film is not particularly limited as long as it is a method capable of producing a thin film. It may be a wet coating method (coating method) other than the method using the auxiliary device used in the examples. By using the coating method, excellent surface smoothness can be obtained. In the coating method, when a small amount is produced, a spin coating method or a bar coating method capable of easily and uniformly forming a film can be mentioned. In the case of roll-to-roll in which productivity is important, examples include a gravure coating method, a die coating method, a reverse coating method, a roll coating method, a slit coating method, a dipping method, and spray coating. Method, anastomotic coating method, reverse anastomotic coating method, air knife coating method, curtain coating method, rod coat method, inkjet method, and the like. In addition, a method using various printing devices such as a letterpress printing method, a gravure printing method, a lithographic printing method, and a stencil printing method can be cited. What is necessary is just to select from these methods suitably according to the required thickness, viscosity, hardening conditions, etc.

12 OLED element The OLED element of the present invention includes the resin film of the present invention. The OLED element may be any one of rigidity and flexibility. The excellent flexibility of the resin film is more suitable for a flexible type element. Furthermore, since the resin film of the present invention has excellent transparency and heat resistance, it can replace a conventional glass substrate and polyethylene naphthalate (bottom emission) type flexible OLED element ( Polyethylene naphthalate (PEN) film substrate is used as a transparent substrate. Alternatively, it can be laminated on or under a conventional substrate and used as an impact absorbing film. It can be used as a sealing film in a top emission type flexible OLED device instead of a sealing glass. Alternatively, it can be laminated on or under a conventional sealing glass to be used as an impact absorbing film. Alternatively, it can be used as a transparent substrate instead of the previous glass substrate, polyimide (PI) film substrate, and polyethylene naphthalate (PEN) substrate. Although ordinary polyurea resins are excellent in properties such as heat resistance and mechanical strength, the isocyanate component has high reactivity with the amine component, and the cured product is insoluble in general organic solvents. Therefore, its use form is limited, and it is difficult to apply it to applications requiring precise coating. Field of electronic information materials. However, since a polyurea resin that is soluble in general organic solvents is synthesized according to the present invention, it can be used in a desired place by coating the resin composition and drying it, and can be applied to the field of electronic information. Since the OLED element of the present invention includes a layer that absorbs impact, it is possible to prevent breakage of the OLED element.

13 Light-emitting device The light-emitting device of the present invention includes the OLED element of the present invention. Examples of the light-emitting device include organic EL displays, particularly flexible organic EL displays, organic EL lighting, and especially flexible organic EL lighting. The organic EL display is not particularly limited as long as it includes the OLED element of the present invention. Examples include televisions, mobile information terminals, wearable systems, car displays, digital signage, and the like. According to the present invention, since the shock absorbing layer is provided, it is possible to prevent the failure of the light emitting device due to the breakage of the OLED element. [Example]

Hereinafter, the present invention will be further specifically described using examples, but the present invention is not limited to the following examples.

The meanings of the symbols used in the examples are as follows. PSt: Polystyrene (manufactured by PSS Polymer Standards Service) BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane (Wakayama Fine Chemical Industry Co., Ltd. (Manufactured) DMAc: N, N-dimethylacetamide (manufactured by Kanto Chemical Co., Ltd., dehydrated) THF: tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography) DMF: N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for HPLC) DEF: N, N-diethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) HXDI: 1 , 3-bis (isocyanate methyl) cyclohexane (product name manufactured by Mitsui Chemicals: Takenate 600) Solmix AP-1: ethanol, 2-propanol, Methanol, water mixture (manufactured by Nippon Alcohol Sales) Silaplane FM4411: hydroxyl modified silicon compound at both ends, hydroxyl equivalent: 564 g / mol (manufactured by JNC) Silaplane FM3311: α, ω- (3-Aminopropyl) polydimethylsiloxane (manufactured by JNC) Orgatix ZC-150: Tetraacetamidine Zirconyl pyruvate (manufactured by Matsumoto Fine Chemical Co., Ltd.) Mw: weight average molecular weight polydispersity index (PDI) (Mw / Mn): molecular weight distribution index

Next, analysis conditions in the manufacturing examples and the examples are shown. <Gel Permeation Chromatography (GPC)> Device: LC-2000Plus series (detector: differential refractive index meter) manufactured by JASCO Corporation. Solvent: THF / DMF = 1/1 (v / v) Flow rate: 0.5 ml / min. Column temperature: 40 ° C. Column used: Asahipak GF-1G 7B (protection column) + Asahipak GF-7M HQ manufactured by Showa Denko Co., Ltd., except for limiting molecular weight (PEG) = 10,000,000 calibration curve Standard sample: PSt

1 Block copolymer [Production Example 1] Synthesis of alternating copolymer (1) Under a nitrogen atmosphere, BAPP (14.3 g) and DMAc (57.4 g) were introduced into a 200 equipped with a reflux cooler, a thermometer, and a dropping funnel. mL of a three-necked flask. It was heated to 120 ° C using an oil bath. Then, a solution in which HXDI (5.66 g) was dissolved in DMAc (22.6 g) was introduced together with a syringe (syringe), and a reaction was started (HXDI: BAPP = 1.0: 1.2, Molar ratio). After that, the temperature was kept at 120 ° C. and stirred for 6 hours to obtain a transparent reaction liquid. The Mw obtained by GPC analysis of the reaction solution was 8,200, and the PDI was 2.7. Furthermore, Solmix AP-1 (600 mL) was prepared in a 1 L beaker, and the obtained polymerization solution (20 mL) was slowly added dropwise while stirring with a stirrer. . A white solid precipitated in the solution. The precipitate was recovered by suction filtration, and then dried in a vacuum dryer set at 120 ° C. for 6 hours to obtain the target alternating copolymer (1).

[Production Example 2] Synthesis of alternating copolymer (2) Under a nitrogen atmosphere, HXDI (51.1 g) and DMAc (249.0 g) were introduced into a 1,000 mL three-necked flask equipped with a reflux cooler, a thermometer, and a dropping funnel. . The flask was immersed in a water bath and maintained in a cooled state. A solution in which Silaplane FM4411 (198.8 g) was dissolved was added dropwise using a dropping funnel, and the reaction was started (HXDI: FM4411 = 1.5: 1, mole ratio). . Thereafter, the reaction was continued for 6 hours to obtain a transparent reaction solution. The Mw of the reaction solution obtained by GPC analysis was 6,100 and the PDI was 1.9, and the target alternating copolymer (2) was obtained.

[Production Example 3] Synthesis of alternating copolymer (3) Under a nitrogen atmosphere, HXDI (4.26 g) and DMAc (57.6 g) were introduced into a 200 mL three-necked flask equipped with a reflux cooler, a thermometer, and a dropping funnel. . Then, it heated at 40 degreeC using the oil bath. A solution prepared by adding DMAc (14.4 g) to FM3311 (13.74 g) was added dropwise, and the reaction was started (HXDI: FM3311 = 1.5: 1, Molar ratio). Then, it stirred at 40 degreeC for 5 hours, and obtained the transparent reaction liquid. The Mw of the reaction solution obtained by GPC analysis was 9,900 and the PDI was 3.2, and the target alternating copolymer (3) was obtained.

[Manufacturing Example 4] Synthesis of Alternating Copolymer (4) DMAc (750.6 g) was introduced into the alternating copolymer (2) synthesized in [Manufacturing Example 2], and the concentration was adjusted to 20%. Furthermore, methanol (8.4 g) was introduced and stirred for 30 minutes, thereby reacting the terminal isocyanate group of the alternating copolymer (2) with methanol and inertizing it, thereby obtaining an alternating copolymer (4).

[Manufacturing Example 5] Synthesis of Alternating Copolymer (5) Methanol (0.7 g) was introduced into a reaction solution obtained by heating the alternating copolymer (3) synthesized in [Manufacturing Example 3] at 40 ° C, and stirred for 30 minutes. By this, the terminal isocyanate group of the alternating copolymer (3) was reacted with methanol, and inertization was performed, thereby obtaining the alternating copolymer (5).

[Example 1] Synthesis of block copolymer (1) Under a nitrogen atmosphere, the alternating copolymer (1) (5.02 g) obtained in [Production Example 1] was introduced into a reflux cooler, a thermometer, and a drip tube. A three-necked flask (200 mL) of a liquid funnel was then charged with DMAc (20.0 g). After heating to 120 ° C using an oil bath, the alternating copolymer (2) (30.0 g) and DMAc (45.1 g) obtained in [Production Example 2] were introduced into a dropping funnel (copolymer concentration: 20%) . After that, the dropwise addition was started quickly, and the alternating copolymer (1) and the alternating copolymer (2) were mixed uniformly in the flask while being stirred (the alternating copolymer (1): the alternating copolymer (2) = 1: 3, weight ratio) . The block copolymer (1) was obtained by stirring and reacting at 120 degreeC for 6 hours. The obtained reaction solution was transparent, and the Mw determined by GPC analysis was 61,000 and the PDI was 6.0.

[Example 2] Synthesis of block copolymer (2) Under a nitrogen atmosphere, the alternating copolymer (3) (75.0 g) obtained in [Production Example 3] was introduced into a reflux cooler, a thermometer, and a drip tube. Liquid funnel in a three-necked flask (200 mL). It was then heated to 120 ° C using an oil bath. A solution prepared by mixing 5.00 g of the alternating copolymer (1) obtained in [Production Example 1] with DMAc (20.0 g) was introduced into a dropping funnel (copolymer concentration: 20%). Then, the dropwise addition was started quickly, and the alternating copolymer (1) and the alternating copolymer (3) were uniformly mixed in the flask while stirring (the alternating copolymer (1): the alternating copolymer (3) = 1: 3, weight ratio) . The block copolymer (2) was obtained by stirring and reacting at 120 degreeC for 6 hours. The obtained reaction solution was transparent, and Mw calculated by GPC analysis was 132,000 and PDI was 15.9.

[Example 3] 1.0 g of a reaction solution containing the block copolymer (1) synthesized in [Example 1] was coated on an aluminum substrate, and heated on a hot plate heated at 120 ° C for 1 hour to The solvent was distilled off to obtain a transparent homogeneous film (1). When the film (1) was peeled from the aluminum substrate, a transparent and homogeneous self-supporting film was obtained.

[Example 4] 1.0 g of a reaction solution containing the block copolymer (2) synthesized in [Example 2] was coated on an aluminum substrate, and heated on a hot plate heated to 120 ° C for 1 hour to The solvent was distilled off to obtain a transparent homogeneous film (2). When the film (2) was peeled from the aluminum substrate, a transparent and homogeneous self-supporting film was obtained.

[Comparative Example 1] Production of film (3) mixed with alternating copolymer (1) and alternating copolymer (4) DMAc 4.02 g was added to 1.00 g of alternating copolymer (1) synthesized in [Production Example 1] A solution having a solid content concentration of 20 wt% was prepared. In addition, a 20 wt% solution of the alternating copolymer (1) and the alternating copolymer (4) synthesized in [Production Example 4] were used to form the alternating copolymer (1): the alternating copolymer (4) = 1: 3 ( Weight ratio). The mixed solution was a cloudy and uneven solution. The mixed solution (1.00 g) was coated on an aluminum substrate and heated on a hot plate heated to 120 ° C. for 1 hour to distill off the solvent. As a result, a cloudy film (3) was obtained. The film (3) was peeled from the aluminum substrate, and as a result, a self-supporting film could not be obtained.

[Comparative Example 2] Production of film (4) mixed with alternating copolymer (1) and alternating copolymer (5) DMAc 4.02 g was added to 1.00 g of alternating copolymer (1) synthesized in [Production Example 1] A solution having a solid content concentration of 20 wt% was prepared. In addition, a 20 wt% solution of the alternating copolymer (1) and the alternating copolymer (5) synthesized in [Production Example 5] were used to make the alternating copolymer (1): the alternating copolymer (5) = 1: 3 ( Weight ratio). The mixed solution was a cloudy and uneven solution. The mixed solution (1.00 g) was coated on an aluminum substrate and heated on a hot plate heated at 120 ° C. for 1 hour to distill off the solvent. As a result, a cloudy film (4) was obtained. The film (4) was peeled from the aluminum substrate, and as a result, a self-supporting film could not be obtained.

[Table 1]

As can be seen from Table 1, Example 3 and Example 4 are significantly different from Comparative Example 1 and Comparative Example 2, and it can be seen that the target block copolymer was obtained.

2 Resin film [Production Example 11] Synthesis of polymer (11) as an alternating copolymer Under a nitrogen atmosphere, BAPP (4.06 g) was placed in a 100 ml three-necked flask equipped with a reflux cooler and a thermometer, and added DEF (17 ml), dissolve using a stir bar. Use an oil bath to heat to 120 ° C. Then, use a funnel to add a solution prepared by dissolving HXDI (1.94 g) in DEF (5.3 ml) in a 30 ml sample bottle (BAPP: HXDI = 1: 1.01, Morse ratio). The DEF solution of HXDI remaining in a 30 ml sample bottle was washed with DEF (2.9 ml), and added to the reaction solution. Thereafter, the reaction was maintained at 120 ° C. for 4 hours, followed by cooling in a water bath, and 1 ml of methanol was added to quench excess isocyanate groups. The Mw obtained by GPC analysis of the reaction solution was 126,000 and the PDI was 20.0, and a polymer (11), which is a polyurea-based alternating copolymer including the structural unit of the target alternating copolymer, was obtained.

[Production Example 12] Synthesis of polymer (12) as an alternating copolymer Under a nitrogen atmosphere, HXDI (2.7 g) and DMAc (50.1 g) were introduced into 200 mL equipped with a reflux cooler, a thermometer, and a dropping funnel. Three-necked flask. The flask was immersed in a water bath and maintained in a cooled state, and Silaplane FM3311 (12.3 g) was added dropwise using a dropping funnel (HXDI: FM3311 = 1.06: 1, Morse ratio). Further, FM3311 attached to the dropping funnel was rinsed with DMAc (10.0 g) and introduced into the flask. Thereafter, the reaction was continued for 2 hours to obtain a transparent reaction solution. The Mw obtained by GPC analysis of the reaction solution was 34,000 and the PDI was 7.0. The polymer (12), which is a polyurea-based alternating copolymer containing the structural unit of the target alternating copolymer, was obtained.

[Production Example 13] Synthesis of Alternating Copolymer 1 represented by Synthesis Formula (1) of Polymer (13) as a Block Copolymer: BAPP (71.7 g) and DMAc (287.0 g) were introduced under a nitrogen atmosphere. Into a 1000 mL three-necked flask equipped with a reflux cooler, thermometer, and dropping funnel. Use an oil bath to heat to 120 ° C. Then, a solution prepared by dissolving HXDI (28.3 g) in DMAc (113.8 g) was introduced into a dropping funnel and dropped into a flask, and the reaction was started (HXDI: BAPP = 1.0: 1.2, Molar ratio) . Thereafter, the temperature was maintained at 120 ° C. and the mixture was stirred for 5 hours to obtain a transparent reaction solution. The Mw obtained by GPC analysis of the reaction solution was 17,000, and the PDI was 3.5. Furthermore, in a 3 L beaker, a mixed solution of Solmix AP-1 (2160 mL) and acetone (240 ml) was prepared, which was obtained by using a stirrer while slowly adding paste. Polymer solution (82 g). A white solid precipitated in the solution. The precipitate was recovered by suction filtration. This operation was performed 4 times to obtain a white solid including a solvent. The obtained white solid was dried in a vacuum dryer set at 120 ° C. for 6 hours to obtain 59 g of the alternating copolymer 1 represented by the formula (1) as a target.

Synthesis of Alternating Copolymer 2 represented by Formula (2-1): Under a nitrogen atmosphere, introduce HXDI (23.7 g) and DMAc (310.2 g) into a 1000 mL container equipped with a reflux cooler, a thermometer, and a dropping funnel. Three-necked flask. Then, it heated at 40 degreeC using the oil bath. A solution prepared by adding DMAc (80.2 g) to FM3311 (73.3 g) was added dropwise, and the reaction was started (HXDI: FM3311 = 1.5: 1, Molar ratio). Then, it stirred at 40 degreeC for 6 hours, and obtained the transparent reaction liquid. The Mw obtained by GPC analysis of the reaction solution was 11,000, and the PDI was 4.0. A reaction solution of the alternating copolymer 2 represented by the target formula (2-1) was obtained.

Synthesis of block copolymer: Under a nitrogen atmosphere, a reaction solution (375.0 g) of the alternating copolymer 2 represented by formula (2-1) was introduced into a three-necked flask (equipped with a reflux cooler, a thermometer, and a dropping funnel) 1000 mL). Then, it heated at 120 degreeC using the oil bath. A solution prepared by mixing 24.9 g of the alternating copolymer 1 represented by the formula (1) and DMAc (119.5 g) was introduced into a dropping funnel (copolymer concentration: 19%). After that, the dropwise addition was started quickly, and the alternating copolymer 1 and the alternating copolymer 2 were stirred and uniformly mixed in the flask and reacted (alternating copolymer 1: alternating copolymer 2 = 1: 3, weight ratio). The polymer (13), which is a target block copolymer, was obtained by stirring at 120 ° C for 5 hours. The obtained reaction solution was transparent, and Mw calculated by GPC analysis was 98,000 and PDI was 9.3.

[Production Example 14] to [Production Example 17] Synthesis of polymer (14) to polymer (17) except for the composition such as molar ratio, weight ratio, etc., and quenching by adding methanol during the reaction of the block copolymer, Polymer (14) to polymer (17) as block copolymers having different molecular weights were synthesized by the method according to [Production Example 13].

[Production Example 18] to [Production Example 20] Synthesis of polymer (18) to polymer (20) In addition to the composition such as mole ratio and weight ratio, FM3311 was changed to FM4411 to the total weight of HXDI and FM4411 After adding 0.5 wt% of Orgatix ZC-150 as a catalyst, the reaction was performed at 80 ° C to obtain a reaction solution of the alternating copolymer 2 represented by formula (2-2). [Production Example 14] to [Production Example 17] The polymers (18) to (20) having different molecular weights were synthesized.

[Production Example 21] Synthesis of Polymer (21) A polymer (21), which is a target block copolymer, was synthesized by a method according to [Production Example 15] except that the molar ratio and the reaction scale were different.

[Production Example 22] The synthesis of the polymer (22) was carried out in accordance with [Production Example 19] except that the reaction temperature of the alternating copolymer 2 represented by Formula (2-2) was set to 25 ° C. in addition to the molar ratio and reaction scale. ] Method to synthesize the target block copolymer, polymer (22).

Table 2 shows the compositions, Mw, and PDI of the polymers (11) to (22) obtained. [Table 2]

[Example 11] Production of resin film (11) A release film (product name: NSD-100, 100 μm, manufactured by Fujimori Industry Co., Ltd.) was used as a base material. The polymer (11) (concentration: 19%, solvent: DEF) synthesized in Production Example 11 was casted on a substrate, and a Baker-type membrane auxiliary device (product name: No. 510 Baker-type film auxiliary device, Yasuda) was adjusted. The scales on both sides of Seiki (strand) are adjusted and the distance between the gap between the auxiliary device and the substrate is adjusted to produce a coating film with a uniform film thickness. After drying at 120 ° C for 15 minutes, the release film was removed to obtain a single-layer tree resin film (11) having a film thickness of 40 μm.

[Example 12] to [Example 20] Production of resin film (12) to resin film (20) Instead of polymer (11), polymer (12) to polymer (20) were used, and the scale of the auxiliary device was changed In addition, the concentration, and the solvent, a single-layer resin film (12) to a resin film (20) were obtained by the method according to Example 11.

Table 3 shows the characteristics and film thickness of the obtained single-layer resin film. [table 3]

[Comparative Example 11] The transparent polyfluorene imide (film thickness: 50 μm) was also subjected to the following tests. [Comparative Example 12] In the case where no resin film was left, it was similarly used in the following test.

<Impact absorption test> A chrome steel ball (model: CR-3 / 4, material: chrome steel (SUJ-2), size: 3/4 inch, manufactured by ASONE) is 10 cm in height Fall down everywhere. A sample of the resin film was placed at the drop position, and SUS430 (0.5 cm thick) was set below it. A general-purpose piezoelectric load cell (type: 208C05, made by PCB Piezotronics) is set under the SUS430, and an oscilloscope (model: DS-5107B, Iwasaki communication unit (stock) (Manufacture)) The impact force applied to the resin film sample when it was dropped was measured. A signal conditioner (type: 480C02, made by PCB Piezotronics) is connected between the general piezoelectric load cell and the oscilloscope. For the resin film samples, prepare slide glass (product name: ASLAB, MICROSCOPE SLIDES), 25 mm × 75 mm, thickness: 1 mm, ASONE (Manufactured)) cut into a length of about 25 mm × 30 mm, and the resin film is placed above or below the glass.

<Glass protective test> The state of the glass after the impact absorption test was observed. In addition, when the glass is broken, it is considered that part of the impact force contributes to the breakage of the glass, and therefore it cannot be measured in the impact absorption test.

The results of the single-layer resin film of Examples 11 to 20, the single-layer transparent polyfluorene imine of Comparative Example 11, and the results of the impact absorption test and glass protection test of the glass of Comparative Example 12 are shown below. . [Table 4] [table 5]

Test results: From Tables 4 and 5, it is clear that if only glass is used, the glass breaks by falling balls, but not only when the resin films of Examples 11 to 20 are placed on top of the glass, It also functions as a protective glass when placed underneath. In addition, as for the transparent polyimide, it is known that the glass breaks when the film is placed above the glass, and does not break when the film is placed below. Therefore, the function of protecting the glass is better than that of the resins of Examples 11 to 20 The film is small.

[Example 21] Production of a resin film (21) including a laminate of a polymer (21) / polymer (22) / polymer (21) The formation of a resin layer 11 was adjusted in advance: The polymer (21) (concentration: 20%, solvent: DMAc) of the alternating copolymer 2 of formula (2-1) was distilled to remove the solvent under reduced pressure to prepare a solution having a concentration of 42% for use. A release film was used as a substrate. The polymer (21) (concentration: 42%) was cast on a substrate, and a variable Baker film adjuvant (type: 3530/6, manufactured by Elcometer) was used to produce a coating film having a uniform film thickness. After drying at 120 ° C. for 15 minutes, a resin layer 11 having a film thickness of 35 μm was obtained.

Formation of Resin Layer 12: The polymer (22) (concentration: 20%, solvent: DMAc) containing the alternating copolymer 2 of formula (2-2) synthesized in Production Example 22 was further distilled under reduced pressure. The solvent was removed, and a solution having a concentration of 46% was applied to the resin layer 11. An auxiliary device (product name: No. 510 Baker-type film auxiliary device, manufactured by Yasuda Seiki Co., Ltd.) was used to produce a coating film having a uniform film thickness. After drying at 120 ° C for 15 minutes, a resin layer 12 was obtained as a two-layer film (total film thickness: 65 μm) containing the polymer (21) / polymer (22).

Formation of resin layer 13: production of laminated resin film (21) Further, polymer (21) (concentration: 42%) was cast on resin layer 12 using an auxiliary device (product name: No. 510 Baker-type film auxiliary device, (Made by Yasuda Seiki Co., Ltd.) to produce a coating film with a uniform film thickness. After drying at 120 ° C for 15 minutes, a resin layer 13 was obtained as a three-layer film (total film thickness: 100 μm) containing the polymer (21) / polymer (22) / polymer (21). The release film is removed, thereby forming a laminated resin film (21).

[Example 22] Preparation of resin film (22) including polymer (22) / polymer (21) / polymer (22) laminated resin layer 14 formation The polymer (22) (concentration: 20%, solvent: DMAc) of the alternating copolymer 2 of formula (2-2) was distilled to remove the solvent under reduced pressure to prepare a solution having a concentration of 46% and used. A release film was used as a substrate. The polymer (22) (concentration 46%) was cast on a substrate, and a variable Baker film adjuvant (type: 3530/6, manufactured by Elcometer) was used to produce a coating film having a uniform film thickness. After drying at 120 ° C. for 15 minutes, a resin layer 14 having a film thickness of 35 μm was obtained.

Formation of resin layer 15: Further, polymer (21) (concentration: 20%, solvent: DMAc) containing the alternating copolymer 2 of formula (2-1) synthesized in Production Example 21 was distilled under reduced pressure. The solvent was removed and a 42% concentration solution was applied to the resin layer 14. An auxiliary device (product name: No. 510 Baker-type film auxiliary device, manufactured by Yasuda Seiki Co., Ltd.) was used to produce a coating film having a uniform thickness. After drying at 120 ° C for 15 minutes, a resin layer 15 was obtained as a two-layer film (total film thickness: 65 μm) containing the polymer (22) / polymer (21).

Formation of Resin Layer 16: Production of Laminated Resin Film (22) Further, the polymer (22) (concentration: 20%, solvent: DMAc) synthesized in Production Example 22 was prepared by distilling off the solvent under reduced pressure. A solution having a concentration of 46% was applied to the resin layer 15 and an auxiliary device (product name: No. 510 Baker-type film auxiliary device, manufactured by Yasuda Seiki Co., Ltd.) was used to produce a coating film having a uniform film thickness. After drying at 120 ° C for 15 minutes, a resin layer 16 was obtained as a three-layer film (total film thickness: 100 μm) containing the polymer (22) / polymer (21) / polymer (22). The release film is removed, thereby forming a laminated resin film (22).

[Example 23] Preparation of single-layer resin film (23) using polymer (21) The polymer (21) (concentration: 20%, solvent: DMAc) synthesized in Production Example 21 was adjusted in advance under reduced pressure. The solvent was removed by distillation to make a 50% solution and used. A release film was used as a substrate. The polymer (21) (concentration: 50%) was cast on a substrate, and an auxiliary device (product name: No. 510 Baker-type film auxiliary device, manufactured by Yasuda Seiki Co., Ltd.) was used to produce a coating film having a uniform film thickness. After drying at 120 ° C for 15 minutes, the release film was removed to obtain a single-layer resin film (23) having a film thickness of 100 μm.

[Example 24] Production of a single-layer resin film (24) using a polymer (22), except that the polymer (22) was used instead of the polymer (21), and a film thickness of 100 was obtained by the method according to Example 23 μm single-layer resin film (24).

[Example 25] Production of laminated resin film (25) using polymer (21) The polymer (21) (concentration: 20%, solvent: DMAc) synthesized in Production Example 21 was adjusted in advance under reduced pressure The solvent was removed by distillation to make a 50% solution and used. A release film was used as a substrate. The polymer (21) (concentration: 50%) was cast on a substrate, and an auxiliary device (product name: No. 510 Baker-type film auxiliary device, manufactured by Yasuda Seiki Co., Ltd.) was used to produce a coating film having a uniform film thickness. After drying at 120 ° C. for 15 minutes, the release film was removed to obtain a single-layer resin film having a film thickness of 80 μm. Five films were stacked to form a laminated resin film (25) with a total film thickness of 400 μm.

[Example 26] Production of a laminated resin film (26) using a polymer (22) In addition to using the polymer (22) instead of the polymer (21), the method according to Example 25 was used to obtain a total film thickness of 400 μm laminated resin film (26).

Table 6 shows the characteristics and film thickness of the obtained laminated and single-layer resin films. [TABLE 6]

[Comparative Example 13] Two sheets of transparent polyimide (film thickness: 50 μm) (total film thickness: 100 μm) were stacked and used in the following test. [Comparative Example 14] Eight sheets of transparent polyimide (film thickness: 50 μm) (total film thickness: 400 μm) were stacked and used in the following test.

<Impact absorption test> Except that a chrome steel ball was dropped from a height of 30 cm, and glass was removed from a resin film sample in order to avoid the influence of glass breakage, it was performed under the same conditions as in Examples 11 to 20 Impact absorption test. <Glass protection test> In addition to the SUS shallow flat chassis, a resin film was set under the glass, and a chromium ball was dropped using an acrylic tube having a height of 50 cm. In addition, the method according to Example 11 to Example 20 was used to The protective properties of the glass were tested.

The impact absorption test and glass protective property of the laminated or single-layer resin film (film thickness 100 μm) of Comparative Example 13 and the transparent polyfluorene imide (film thickness 100 μm) of Comparative Example 13 are shown below. Test results. [TABLE 7]

Test results: In any of Examples 21 to 24, the impact force was lower than that of Comparative Example 13. The impact force of the laminated film of Example 21 was the smallest.

The results of the impact absorption tests of the laminated resin films (film thickness 400 μm) of the laminates of Examples 25 and 26 and the transparent polyfluorene imide (film thickness 400 μm) of the laminates of Comparative Example 14 are shown below. [TABLE 8]

Test results: In either case of Example 25 and Example 26, the impact force was smaller than that of Comparative Example 14. It is clear that by increasing the film thickness to 400 μm, the impact force can be greatly reduced.

For the publications cited in this specification, and all documents including Japanese patent applications and Japanese patents, each document is specifically shown and incorporated into this case for reference, and the entire contents described in this specification are The same degree is incorporated in the present invention for reference.

The use of nouns and the same designations used in connection with the description of the present invention (especially related to the scope of patent applications below) can be understood as involving singular and plural as long as they are not specifically mentioned in this specification or are not clearly inconsistent with context. Both. The phrases "including", "having", "containing", and "including" can be understood as open-end terms (ie, meaning of "including-but not limited to") unless otherwise specified. The detailed description of the numerical range in this specification is only intended to serve as a notation for referring to each value that falls within the range one by one, as long as it is not specifically mentioned in this specification. The enumeration is incorporated into the description. All the methods described in this specification can be performed in all appropriate order as long as they are not specifically pointed out in this specification or are not clearly contradictory to context. All examples or illustrative words (such as "etc.") used in this specification are only intended to better illustrate the present invention and do not limit the scope of the present invention unless specifically claimed. Any wording in the specification should not be interpreted to mean an element that is not described in the scope of a patent application that is indispensable for implementing the present invention.

In this specification, in order to implement the present invention, a preferred embodiment of the present invention has been described, including the best form known to the inventors. For those skilled in the art, after reading the description, modifications of the preferred embodiments will be clear. The inventor anticipates that a skilled person will appropriately apply such a modification and intends to implement the present invention by a method other than that specifically described in this specification. Therefore, as permitted by the benchmark method, the present invention includes all changes and equivalents described in the scope of patent application accompanying this specification. Furthermore, as long as it is not specifically pointed out in the present specification or is not clearly contradictory to the context, any combination of the elements in all variations is included in the present invention. [Industrial availability]

The block copolymer of the present invention is useful not only as a matrix resin for a coating material or a film substrate, but also because it has an amine group or an isocyanate group at both ends and also has a urethane bond or a urea bond on the main chain. Therefore, it is extremely useful as a reactive oligomer.

no

FIG. 1 is a photograph showing the appearance of a coating film in Example 4. FIG. FIG. 2 is a photograph showing the appearance of a self-supporting film in Example 4. FIG. FIG. 3 is a photograph showing the appearance of a coating film in Comparative Example 2. FIG. FIG. 4 is a photograph showing the appearance of a self-supporting film in Comparative Example 2. FIG. Fig. 5 is a photo after the test of the glass protective test of Example 11 (a). FIG. 6 is a post-test photograph of the glass protective test of Example 11 (b). FIG. 7 is a post-test photograph of the glass protective test of Example 12 (a). FIG. 8 is a post-test photograph of the glass protective test of Example 12 (b). FIG. 9 is a post-test photograph of the glass protective test of Example 13 (a). FIG. 10 is a post-test photograph of the glass protective test of Example 13 (b). FIG. 11 is a post-test photograph of the glass protective test of Example 14 (a). FIG. 12 is a post-test photograph of the glass protective test of Example 14 (b). FIG. 13 is a photo after the test of the glass protective test of Example 15 (a). FIG. 14 is a post-test photograph of the glass protective test of Example 15 (b). FIG. 15 is a post-test photograph of the glass protective test of Example 16 (a). FIG. 16 is a post-test photograph of the glass protective test of Example 16 (b). FIG. 17 is a post-test photograph of the glass protective test of Example 17 (a). FIG. 18 is a post-test photograph of the glass protective test of Example 17 (b). FIG. 19 is a photo after the test of the glass protective test of Example 18 (a). FIG. 20 is a post-test photograph of the glass protective test of Example 18 (b). FIG. 21 is a post-test photograph of the glass protective test of Example 19 (a). FIG. 22 is a post-test photograph of the glass protective test of Example 19 (b). FIG. 23 is a post-test photograph of the glass protective test of Example 20 (a). FIG. 24 is a post-test photograph of the glass protective test of Example 20 (b). FIG. 25 is a post-test photograph of the glass protective test of Example 21. FIG. FIG. 26 is a post-test photograph of the glass protective test of Example 22. FIG. FIG. 27 is a post-test photograph of the glass protective test of Example 23. FIG. FIG. 28 is a post-test photograph of the glass protective test of Example 24. FIG. FIG. 29 is a post-test photograph of a glass protective test of Comparative Example 11 (a). FIG. 30 is a post-test photograph of a glass protective test of Comparative Example 11 (b). FIG. 31 is a post-test photograph of the glass protective test of Comparative Example 12 (a) and Comparative Example 12 (b). FIG. 32 is a post-test photograph of the glass protective test of Comparative Example 13. FIG.

Claims (16)

A block copolymer, which is an addition polymerization copolymer of the following alternating copolymer 1 and the following alternating copolymer 2 and includes a repeating unit represented by formula (3), and has a weight average molecular weight of 50 to 1 million, The end is any of -NH ₂ , -OH, or -NCO which can be sealed at the end,-[(Alternating copolymer 1)-(Alternating copolymer 2)]-Formula (3) Alternating copolymer 1: Polyurea Is an alternating copolymer, which is an addition polymerization copolymer of a diisocyanate compound <A> and a diamine compound <B>, and contains the formula (1)-[(A)-(B)]-Formula (1) Repeating unit, weight average molecular weight is 500-300,000, both ends are -NH ₂ or -NCO; Alternating copolymer 2: selected from polyurea-based alternating copolymer 2-1 and polyurethane-based alternating copolymer 2 At least one alternating copolymer in -2, the polyurea-based alternating copolymer 2-1 is an addition polymerization copolymer of a diisocyanate compound <A> and a diamine compound <C ¹ >, and contains the formula (2-1 ) - [(a) - ( C 1)] - formula (2-1) repeating units represented by the weight average molecular weight of 500 to 300,000, both ends of -NCO or -NH ₂ The polyurethane-based alternating copolymer 2-2 <A> a diisocyanate compound with a diol compound <C ^2> a copolymer of addition polymerization, and comprising the formula (2-2) - [(A) -(C ² )]-The repeating unit represented by formula (2-2) has a weight average molecular weight of 500 to 300,000 and has -NCO or -OH at both ends; wherein (A) each independently represents that At least one type of aliphatic isocyanate structural unit having a cyclic structure; (B) each independently represents at least one structure selected from the group consisting of an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton. A unit; (C ¹ ) represents at least one structural unit selected from the group consisting of a linear aliphatic diamine, an aliphatic diamine having an ether bond, and a diamine having a siloxane skeleton; (C ² ) representing a linear unit At least one structural unit among the aliphatic aliphatic diol, the aliphatic diol having an ether bond, and the diol having a siloxane skeleton, wherein when both ends of the alternating copolymer 1 are -NCO, the both ends is -NH ₂ or -OH; when both ends of the alternating copolymer 1 ₂ -NH, 2 for both ends of the copolymer is -NCO. The block copolymer according to item 1 of the application, wherein both ends of the alternating copolymer 1 are -NCO, and both ends of the alternating copolymer 2 are -NH ₂ or -OH. The block copolymer according to item 1 of the application, wherein both ends of the alternating copolymer 1 are -NH ₂ and both ends of the alternating copolymer 2 are -NCO. The block copolymer according to any one of claims 1 to 3, wherein the alternating copolymer 2 is a polyurea-based alternating copolymer 2-1. The block copolymer according to any one of claims 1 to 3, wherein the alternating copolymer 2 is a polyurethane-based alternating copolymer 2-2. The block copolymer according to any one of claims 1 to 3, wherein the diisocyanate compound <A> is a compound represented by the following formula (I) to formula (X), In the following formulae (I) to (X), R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen or an alkyl group having 1 to 7 carbon atoms, and X is each independently 1 carbon atom. ~ 7 alkylene, Y are each independently oxygen, sulfur, linear or branched alkylene having 1 to 7 carbon atoms, -C (CF ₃ ) ₂ -or -SO _2- , . A resin composition comprising: the block copolymer according to any one of claims 1 to 6 in the scope of the patent application; and a solvent in which the block copolymer is dissolved. The resin composition according to item 7 of the scope of the patent application, wherein the solvent comprises propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, 4-methyl-2-pentanone, N, N-dimethylpropanidine At least one of an amine, tetramethylurea, and dimethylsulfine. A coating film comprising a solid component obtained by removing the solvent from the resin composition according to item 7 or 8 of the scope of patent application. A resin film formed of a solid component obtained by removing the solvent from the resin composition according to item 7 or 8 of the scope of patent application. A resin film comprising at least two layers of a resin film formed from a solid component obtained by removing the solvent from the resin composition according to item 7 or item 8 of the patent application scope. A resin film comprising: a resin film (H), which is a resin film (H) formed from a solid component obtained by removing the solvent from the resin composition described in item 7 or 8 of the scope of patent application. And the block copolymer is the block copolymer described in item 4 of the patent application scope; and the resin film (S) is obtained by removing the resin composition from the resin composition described in item 11 of the patent application scope The resin film (S) formed by the solid content obtained by the solvent, and the block copolymer is the block copolymer according to item 5 of the patent application scope. The resin film according to item 12 of the scope of patent application, which includes three layers laminated in the order of the resin film (H) / the resin film (S) / the resin film (H). The resin film according to item 12 of the scope of patent application, which comprises three layers laminated in the order of the resin film (S) / the resin film (H) / the resin film (S). An organic light emitting diode element includes the resin film according to any one of the tenth to the fourteenth in the scope of patent application. A light-emitting device includes the organic light-emitting diode element according to item 15 of the scope of patent application.