WO2019054413A1 - Block copolymer, resin composition, coating membrane, resin film, oled element, light-emitting device, and method for manufacturing 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 device, 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 as a highly elastic recovery material assuming flexible device applications in the field of electronic information materials, and a method for producing the same. Furthermore, it relates to materials that can be horizontally deployed in various applications such as automobiles, building materials, life sciences, and the like.

In recent years, the spread of LCD (liquid crystal display) terminals that can be carried and used outdoors has been remarkable, and smartphones, portable terminals represented by PND (personal navigation device), and wearable displays represented by Google Glass An example is given.
Further, with the practical use of organic EL displays, further weight reduction is required, and a method of switching a part of the members from glass or thin film glass to plastic is taken. However, while thin film glass is excellent in heat resistance, it is very easily cracked, and plastics (especially PET, PC, PMMA, cycloolefin etc.) have features of light weight and high transparency, but they are impact resistant and scratch resistant. And other mechanical properties may be poor, and development of new functional plastics has been required.

Patent Document 1 discloses a coating agent excellent in scratch resistance for a glass substrate, and a coating agent excellent in adhesion to glass and scattering prevention (paragraph 0019). However, although the obtained glass coating layer becomes a thing excellent in abrasion resistance and scattering prevention property, when using for the recent smart phone and wearable display, it was inadequate.
On the other hand, Patent Document 2 is a novel roll which has high hardness and toughness which is useful as various rolls such as calender rolls used for papermaking, textiles, magnetic tapes etc., castors and other general molding resins, and is also excellent in heat resistance. Polyurea resin is disclosed (paragraph 0001). However, the technology relates to a general molding resin that is injected into a mold and used, and is not intended to be applied to a film-like portable terminal or the like in terms of handling and the like.
Furthermore, Patent Document 3 can be obtained by heat treatment at a low temperature, has good adhesion to the base material and the sealing material, has improved tin plating resistance, and further can Resistance to heat, solder flux resistance, solvent resistance, chemical resistance, flex resistance, and electrical properties, and can be favorably applied on substrates such as flexible wiring boards, A polyimide siloxane based insulating film composition for forming an insulating film of parts and the like is disclosed. However, this technology assumes application to a flexible wiring substrate, and no consideration has been given to the transparency required for display applications.

Unexamined-Japanese-Patent No. 2006-290696 JP-A-5-194695 Japanese Patent Laid-Open No. 2004-231757

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

Furthermore, since the novel block copolymer of the present invention has an amine or isocyanate at the molecular terminal and has a urea structure or a urethane structure in the molecule, it has, for example, a (meth) acrylate or an epoxy group having an isocyanate group ( It is possible to react with meta) acrylate and to easily introduce a vinyl functional group.

As a result of intensive research to achieve the above object, the present inventor
An alternating copolymer 1 obtained by polyaddition reaction of an aliphatic diisocyanate compound <A> having a cyclic structure in the molecule and a diamine compound <B>,
A polyaddition of an alternating copolymer 2 which is a polyadduct of an aliphatic diisocyanate compound <A> having a cyclic structure in the molecule and a specific diamine compound <C ¹ > or a diol compound <C ² > The inventors have found a block copolymer and a method for producing the same, and have completed the present invention.
Examples of aspects of the invention are given below.

［７］　［１］～［６］のいずれかに記載のブロック共重合体と；
　前記ブロック共重合体を溶解する溶媒と；を含む、樹脂組成物。
［８］　前記溶媒は、プロピレングリコールモノメチルエーテル（１－メトキシ－２－プロパノール）、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジエチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、４－メチル－２－ペンタノン、Ｎ，Ｎ－ジメチルプロピオンアミド、テトラメチルウレア、ジメチルスルホキシドの少なくとも１つを含む、［７］に記載の樹脂組成物。
［９］　［７］または［８］に記載の樹脂組成物から前記溶媒を除去した固形分を含む、塗膜。
［１０］　［７］または［８］に記載の樹脂組成物から前記溶媒を除去した固形分から形成された、樹脂フィルム。
［１１］　［７］または［８］に記載の樹脂組成物から前記溶媒を除去した固形分から形成された樹脂フィルムを少なくとも２層備える、樹脂フィルム。
［１２］　［７］または［８］に記載の樹脂組成物から前記溶媒を除去した固形分から形成された樹脂フィルム（Ｈ）であって、前記ブロック共重合体は、［４］に記載のブロック共重合体である、樹脂フィルム（Ｈ）と；
　［７］または［８］に記載の樹脂組成物から前記溶媒を除去した固形分から形成された樹脂フィルム（Ｓ）であって、前記ブロック共重合体は、［５］に記載のブロック共重合体である、樹脂フィルム（Ｓ）と；を備える、樹脂フィルム。
［１３］　前記樹脂フィルム（Ｈ）／前記樹脂フィルム（Ｓ）／前記樹脂フィルム（Ｈ）の順に積層された３層を備える、［１２］に記載の樹脂フィルム。
［１４］　前記樹脂フィルム（Ｓ）／前記樹脂フィルム（Ｈ）／前記樹脂フィルム（Ｓ）の順に積層された３層を備える、［１２］に記載の樹脂フィルム。
［１５］　［１０］～［１４］のいずれか１項に記載の樹脂フィルム；を備える、ＯＬＥＤ素子。
［１６］　［１５］に記載のＯＬＥＤ素子；を備える、発光装置。 [1] A repeating unit represented by the formula (3), which is a polyaddition copolymer of alternating copolymer 1 below and alternating copolymer 2 below, having a weight average molecular weight of 5,000 to 1,000,000 Block copolymer, which is either -NH ₂ -OH or -NCO, optionally terminated.
-[(Alternate copolymer 1)-(Alternate copolymer 2)]-Formula (3)
Alternating copolymer 1:
A polyaddition copolymer of a diisocyanate compound <A> and a diamine compound <B>, which is represented by the formula (1)
-[(A)-(B)]-Formula (1)
A polyurea-based alternating copolymer containing a repeating unit represented by the following formula, having a weight average molecular weight of 500 to 300,000, and having both ends of -NH ₂ or -NCO;
Alternating copolymer 2:
A polyaddition copolymer of a diisocyanate compound <A> and a diamine compound <C ¹ >, which is represented by the formula (2-1)
-[(A)-(C ¹ )]-Formula (2-1)
And a polyurea-based alternating copolymer 2-1 having a weight average molecular weight of 500 to 300,000 and having both ends of -NCO or -NH ₂ .
And a polyaddition copolymer of a diisocyanate compound <A> and a diol compound <C ² >, which is represented by the formula (2-2)
-[(A)-(C ² )]-Formula (2-2)
And at least one alternating copolymer selected from polyurethane-based alternating copolymers 2-2 having a weight average molecular weight of 500 to 300,000 and having -NCO or -OH at both ends ;
(Wherein (A) is each independently at least one kind of aliphatic isocyanate structural unit having a cyclic structure in the molecule;
(B) each independently represents at least one structural unit selected from an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton;
(C ¹ ) represents at least one structural unit selected from linear aliphatic diamines, aliphatic diamines having an ether bond, and diamines having a siloxane skeleton;
(C ² ) represents at least one structural unit selected from linear aliphatic diols, aliphatic diols having an ether bond, and diols having a siloxane skeleton.
However, when both ends of alternating copolymer 1 are —NCO, both ends of alternating copolymer 2 are —NH ₂ or —OH;
When both ends of alternating copolymer 1 are —NH ₂ , both ends of alternating copolymer 2 are —NCO. )
[2] The block copolymer according to [1], wherein both ends of alternating copolymer 1 are —NCO and both ends of alternating copolymer 2 are —NH ₂ or —OH.
[3] The block copolymer according to [1], wherein both ends of alternating copolymer 1 are —NH ₂ and both ends of 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 alternating copolymer 2-1.
[5] The block copolymer according to any one of [1] to [3], wherein the alternating copolymer 2 is a polyurethane alternating copolymer 2-2.
[6] The diisocyanate compound <A> is a compound represented by the following formulas (I) to (X),
In the following formulas (I) to (X), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or alkyl having 1 to 7 carbon atoms,
X is each independently alkylene having 1 to 7 carbon atoms,
Y is each independently oxygen, sulfur, linear or branched alkylene having 1 to 7 carbon atoms, -C (CF ₃ ) ₂ -or -SO _2-
The block copolymer according to any one of [1] to [5].

[7] The block copolymer according to any one of [1] to [6];
A solvent for dissolving the block copolymer.
[8] The solvent is propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, The resin composition according to [7], which contains at least one of 4-methyl-2-pentanone, N, N-dimethylpropionamide, tetramethylurea and dimethyl sulfoxide.
[9] A coating film comprising a solid content obtained by removing the solvent from the resin composition according to [7] or [8].
The resin film formed from the solid which removed the said solvent from the resin composition as described in [10] [7] or [8].
[11] A resin film comprising at least two layers of a resin film formed from a solid obtained by removing the solvent from the resin composition described in [7] or [8].
[12] A resin film (H) formed from the solid obtained by removing the solvent from the resin composition described in [7] or [8], wherein the block copolymer is a block described in [4] A resin film (H) which is a copolymer;
It is a resin film (S) formed from the solid which removed the said solvent from the resin composition as described in [7] or [8], Comprising: The said block copolymer is a block copolymer as described in [5] A resin film (S); and a resin film.
[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 OLED device comprising the resin film according to any one of [10] to [14].
[16] A light emitting device comprising the OLED device according to [15].

The block copolymer obtained in the present invention is soluble in a general-purpose organic solvent, and exhibits an effect of being excellent in transparency, heat resistance, film forming property, and flexibility.

15 is a photograph showing the appearance of a coated film in Example 4. 5 is a photograph showing the appearance of a free standing film in Example 4. 7 is a photograph showing the appearance of a coated film in Comparative Example 2. It is a photograph which shows the external appearance of the free-standing film in comparative example 2. It is a photograph after the test of the glass protection test of Example 11 (a). It is a photograph after the test of the glass protection test of Example 11 (b). It is a photograph after the test of the glass protection test of Example 12 (a). It is a photograph after the test of the glass protection test of Example 12 (b). It is a photograph after the test of the glass protection test of Example 13 (a). It is a photograph after the test of the glass protection test of Example 13 (b). It is a photograph after the test of the glass protection test of Example 14 (a). It is a photograph after the test of the glass protection test of Example 14 (b). It is a photograph after the test of the glass protection test of Example 15 (a). It is a photograph after the test of the glass protection test of Example 15 (b). It is a photograph after the test of the glass protection test of Example 16 (a). It is a photograph after the test of the glass protection test of Example 16 (b). It is a photograph after the test of the glass protection test of Example 17 (a). It is a photograph after the test of the glass protection test of Example 17 (b). It is a photograph after the test of the glass protection test of Example 18 (a). It is a photograph after the test of the glass protection test of Example 18 (b). It is a photograph after the test of the glass protection test of Example 19 (a). It is a photograph after the test of the glass protection test of Example 19 (b). It is a photograph after the test of the glass protection test of Example 20 (a). It is a photograph after the test of the glass protection test of Example 20 (b). It is a photograph after the test of the glass protection test of Example 21. It is a post-test photograph of the glass protection test of Example 22. It is a post-test photograph of the glass protection test of Example 23. It is a post-test photograph of the glass protection test of Example 24. It is a photograph after the test of the glass protection test of comparative example 11 (a). It is a photograph after the test of the glass protection test of comparative example 11 (b). It is a photograph after the test of the glass protection test of comparative example 12 (a) (b). It is a photograph after the test of the glass protection test of Comparative Example 13.

This application is based on Japanese Patent Application No. 2017-174735 filed on September 12, 2017 and Japanese Patent Application No. 2018-151547 filed on August 10, 2018 in Japan, the contents of which are incorporated herein by reference. Form part of it. The invention will be more fully understood from the following detailed description. Further areas of applicability of the present invention will become apparent as the description proceeds. However, the detailed description and the specific examples are the preferred embodiments of the present invention and are described only for the purpose of illustration. Various changes and modifications are apparent to those skilled in the art from the detailed description within the spirit and scope of the present invention. The applicant does not intend to give the public any of the described embodiments, and modifications, alternatives, which may not be literally included within the scope of the claims, are also included under the equivalent theory. Part of the invention.

Hereinafter, the block copolymer according to the present invention, the method for producing the block copolymer, and their applications will be described in detail. However, the present invention is not limited to the following embodiments.

The block copolymer of the present invention comprises a repeating unit represented by the formula (3), which is a polyaddition copolymer of the following alternating copolymer 1 and the following alternating copolymer 2, and has a weight average molecular weight It is a block copolymer of 5,000 to 1,000,000 and optionally terminated -NH ₂ -OH or -NCO.
-[(Alternate copolymer 1)-(Alternate copolymer 2)]-Formula (3)
However, when both ends of alternating copolymer 1 are —NCO, both ends of alternating copolymer 2 are —NH ₂ or —OH;
When both ends of alternating copolymer 1 are —NH ₂ , both ends of alternating copolymer 2 are —NCO.
The elements constituting this block copolymer will be sequentially described below.

1 alternating copolymer 1
The alternating copolymer 1 is a polyaddition copolymer of a diisocyanate compound <A> and a diamine compound <B>,
Formula (1)
-[(A)-(B)]-Formula (1)
And a polyurea-based alternating copolymer having a weight average molecular weight of 500 to 300,000 and having both ends of -NH ₂ or -NCO.
(Wherein (A) is at least one of aliphatic diisocyanate structural units having a cyclic structure in the molecule, and (B) each independently represents an aromatic diamine, an aromatic diamine having an ether bond, and a cyclic skeleton) At least one selected from structural units of aliphatic diamines having one)

The alternating copolymer 1 is obtained by polyaddition of the diisocyanate compound <A> and the 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 binding site between the structural units (A) and (B) is a urea structure (-NH-CO-NH-).

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

1.1 Diisocyanate Compound <A>
The diisocyanate compound <A> that 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 X) is mentioned.
In the following formulas (I) to (X), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or alkyl having 1 to 7 carbon atoms,
X is each independently alkylene having 1 to 7 carbon atoms,
Y is each independently oxygen, sulfur, linear or branched alkylene having 1 to 7 carbon atoms, -C (CF ₃ ) ₂ -or -SO _2- .

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

Among the above specific examples, diisocyanate compounds represented by formulas (V), (VI) and (VIII) are preferable because of high solubility in solvents. Furthermore, when high transparency and heat resistance are required, diisocyanate compounds represented by formulas (V) and (VI) can be particularly preferably used.

Furthermore, the diisocyanate compound <A> that 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 is disclosed, for example, in JP-A 2016-199694. Compounds that have been mentioned.

Aliphatic diisocyanates having a cyclic structure in the molecule; isophorone diisocyanate, (bicyclo [2.2.1] heptane-2,5-diyl) bismethylene diisocyanate, (bicyclo [2.2.1] heptane-2,6- Diyl) bismethylene diisocyanate, 2β, 5α-bis (isocyanate) norbornane, 2β, 5β-bis (isocyanate) norbornane, 2β, 6α-bis (isocyanate) norbornane, 2β, 6β-bis (isocyanate) norbornane, 2,6- Di (isocyanate methyl) furan, 1,3-bis (isocyanato methyl) cyclohexane, 1,4-bis (isocyanato methyl) cyclohexane, dicyclohexylmethane diisocyanate, 4, 4- isopropylidene bis (cyclohexyl isocyanate) B) cyclohexanediisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2′-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanate-n-butylidene) pentaerythritol, dimer acid diisocyanate, 3,8-bis (Isocyanatomethyl) tricyclodecane, 3,9-bis (isocyanatemethyl) tricyclodecane, 4,8-bis (isocyanatomethyl) tricyclodecane, 4,9-bis (isocyanatomethyl) tricyclodecane, 1,5 -Diisocyanatedecalin, 2,7-diisocyanatedecalin, 1,4-diisocyanatedecalin, 2,6-diisocyanatedecalin, dicyclohexyl sulfide-4,4'-di Isocyanate, tricycloalkyl thia-octane diisocyanate

The diisocyanate compounds described above may be used alone or in combination of two or more.

1.2 Diamine compound <B>
The diamine compound <B> that can be used in the present invention is not particularly limited as long as it is a diamine compound independently selected from an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton. It is not a thing. For example, diamine compounds disclosed in JP-A-2014-65921 can be used.

The "aliphatic diamine having a cyclic skeleton" means that an amino group is directly bonded to a linear or branched aliphatic hydrocarbon, and has a cyclic structure in the molecule, and an amino group in the molecule. Is a compound having two. The "aromatic diamine" is a compound having two amino groups in the molecule, in which an amino group is directly bonded to carbon of the aromatic ring.

In particular, the diamine compound <B> that can be used to impart high heat resistance is a diamine compound selected from aromatic diamines, aromatic diamines having an ether bond, and aliphatic diamines having a cyclic skeleton, Specific examples include 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 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-phenylene Amine, 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-aminobenzyl) phenyl] Cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] 4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4 4-Aminobenzyl) phenyl] -4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] Tan, 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-diaminocyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4′-diaminodicyclohexylmethane and the like.

Among the above specific examples, 4,4′-diaminodiphenylmethane, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (Aminomethyl) cyclohexane and 4,4'-diaminodicyclohexylmethane are preferable in terms of heat resistance and mechanical properties, and 4,4'-diaminodiphenylmethane and 2,2-bis [4- (4-aminophenoxy) phenyl] Propane can be used particularly preferably.

In particular, examples of the diamine compound <B> that can be used to impart high heat resistance include aliphatic diamines having a cyclic skeleton represented by formulas (XIII-1) and (XIII-2).

  For example, aliphatic diamines having cyclic skeletons represented by formulas (XIV-1) to (XIV-3) can be mentioned.

  For example, aromatic diamines represented by formulas (XV-1) to (XV-5) can be mentioned.

  For example, aromatic diamines represented by formulas (XVI-1) to (XVI-12) and formulas (XVI-20) to (XVI-30), and formulas (XVI-13) to (XVI-19) And aromatic diamines having an ether bond.

  For example, aromatic diamines represented by formulas (XVII-1) to (XVII-4) and aromatic diamines having ether bonds represented by formulas (XVII-5) and (XVII-6) can be given.

  For example, aromatic diamines represented by formulas (XVIII-1) to (XVIII-7) and aromatic diamines having ether bonds represented by formulas (XVIII-8) to (XVIII-11) can be given.

In addition, diamine compound <B> of this invention is not limited to the diamine of this specification, The diamine of various forms can be used in the range which the objective of this invention is achieved. Moreover, only 1 type may be used for the diamine compound of the above-mentioned description, and 2 or more types may be mixed and used.

2 alternating copolymer 2
The alternating copolymer 2 is a polyaddition copolymer of a diisocyanate compound <A> and a diamine compound <C ¹ >,
Formula (2-1)
-[(A)-(C ¹ )]-Formula (2-1)
And a polyurea-based alternating copolymer 2-1 having a weight average molecular weight of 500 to 300,000 and having both ends of -NCO or -NH ₂ .
And a polyaddition copolymer of a diisocyanate compound <A> and a diol compound <C ² >, which is represented by the formula (2-2)
-[(A)-(C ² )]-Formula (2-2)
And a polyurethane-based alternating copolymer 2-2 having a weight average molecular weight of 500 to 300,000 and having -NCO or -OH at both ends.
And at least one alternating copolymer selected from
(Wherein (A) is each independently at least one kind of aliphatic isocyanate structural unit having a cyclic structure in the molecule;
(C ¹ ) represents at least one structural unit selected from linear aliphatic diamines, aliphatic diamines having an ether bond, and diamines having a siloxane skeleton;
(C ² ) represents at least one structural unit selected from linear aliphatic diols, aliphatic diols having an ether bond, and diols having a siloxane skeleton. )

As the alternating copolymer 2, any of the polyurea alternating copolymer 2-1 represented by the formula (2-1) and the polyurethane alternating copolymer 2-2 represented by the formula (2-2) You may use it and you may use both together.

Alternating copolymer 2 is obtained by polyaddition of diisocyanate compound <A> and diamine compound <C ¹ > or diol compound <C ² >. Diisocyanate compound <A>, diamine compound <C ¹ > and diol compound <C ² > correspond to structural unit (A), structural units (C ¹ ) and (C ² ) in alternating copolymer 2, respectively. The bonding site between the structural units (A) and (C ¹ ) is a urea structure (-NH-CO-NH-), and the bonding site between the structural units (A) and (C ² ) is a urethane structure (-NH-CO) It becomes -O-).

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

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

2.2 Diamine Compound <C ¹ > and Diol Compound <C ² >
Any of diamine compounds <C ¹ > or diol compounds <C ² > used for alternating copolymer 2 may be selected, and polyurea-based alternating compounds are obtained by polyaddition of each with diisocyanate compound <A>. The copolymer 2-1 and the polyurethane-based alternating copolymer 2-2 can be obtained. Further, the diamine compound <C ¹ > and the diol compound <C ² > may be used in combination, and in this case, the alternating copolymer 2 is a copolymer simultaneously containing a urea structure and a urethane structure.

2.2.1 Diamine compound <C ¹ >
The diamine compound <C ¹ > is at least one selected from a linear aliphatic diamine compound, an aliphatic diamine compound having an ether bond, and a diamine compound having a siloxane skeleton. For example, compounds disclosed in JP-A-2014-65921 can be used.

The “aliphatic diamine” of the present invention is a linear or branched aliphatic hydrocarbon or a compound having two amino groups in the molecule, in which an amino group is directly bonded to carbon of an aliphatic ring. It is.

  In particular, diamine compounds <C ¹ > that can be used to impart high transparency are diamine compounds selected from linear aliphatic diamines, aliphatic diamines having an ether bond, and diamines having a siloxane skeleton, Specific examples thereof include 1,4-diaminobutane, 1,6-diaminohexane, 1,12-diaminododecane, 1,2-bis (2-aminoethoxy) ethane, diethylene glycol bis (3-aminopropyl) ether, 1 2,4-butanediol bis (3-aminopropyl) ether, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, diamine compounds having a siloxane skeleton represented by the following formula (XI), and the like. .

In the formula, R ₅ and R ₆ are independently alkyl or phenyl having 1 to 3 carbon atoms, R ₇ is independently methylene, phenylene or phenylene in which at least one hydrogen is replaced by alkyl, and x is Independently, it is an integer of 1 to 6, and y is an integer of 0 to 70.

Among the above specific examples, 1,12-diaminododecane, diethylene glycol bis (3-aminopropyl) ether, and diamine compounds having a siloxane skeleton of the formula (XI) are preferable in terms of transparency and mechanical properties, and diethylene glycol bis (3 Particularly preferred are diamine compounds having a -aminopropyl) ether, and a siloxane skeleton of formula (XI).

 
　式（XII－７）中、ｎは１～３０の整数であり、式（XII－８）中、ａは０～２０、ｂは０～７０、ｃは１～９０である。 In particular, as a diamine compound <C ¹ > that can be used to impart high transparency, for example, linear aliphatic diamines represented by formulas (XII-1) to (XII-3), a compound of formula (XII) And aliphatic diamines having an ether bond represented by -4) to (XII-8).

In the formula (XII-7), n is an integer of 1 to 30, and in the formula (XII-8), a is 0 to 20, b is 0 to 70, and c is 1 to 90.

As an aliphatic diamine which has an ether bond represented by Formula (XII-8), Mitsui Chemicals Fine Co., Ltd. product trade name: Jeffamine D-230 (a = 0, b = 0, c = 2), for example Jeffamine D series such as ~ 3), D-400 (a = 0, b = 0, c = 5 to 6), D-2000 (a = 0, b = 0, c = approx. 33), D-4000, etc. 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) Jeffamine ED series such as .0); etc. can be used.

2.2.2 Diol Compound <C ² >
The diol compound <C ² > is at least one selected from 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 above diamine compound <C ¹ > are replaced by —OH can be used.

Mentioned diol compound Specific examples of <C ^2> shown below, but the invention is not limited to these examples.
As the alkylene diol or polyoxyalkylene diol compound, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,7-heptanediol, 1,6-hexanediol, hexylene glycol, neopentyl glycol, Poly 1,2-butylene glycol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol 1,4-cyclohexane Methanol, methyl pentanediol modified polytetramethylene glycol, propylene glycol modified polytetramethylene glycol, ethylene glycol-propylene glycol block copolymer, ethylene glycol-tetramethylene glycol copolymer, 2-methyl-1,8-octanediol, 1,9 -Nonanediol, 3-methyl-1,5-pentanediol, Cylaplane FM4401 (manufactured by JNC Ltd., both terminal hydroxyl modified silicon compound), Cylaplane FM4411 (manufactured by JNC Corporation, both terminal hydroxyl modified silicon compound, Mn = 1000), Silaprene FM 4421 (manufactured by JNC, both-end hydroxyl modified silicon compound, Mn = 5000), Silaprene FM 4425 (manufactured by JNC, both) End hydroxyl modified silicon compound, Mn = 10000) and the like. These are used alone or in combination of two or more.

3 Block copolymer The block copolymer of the present invention comprises a repeating unit represented by the formula (3), which is a polyaddition copolymer of the above-mentioned alternating copolymer 1 and alternating copolymer 2 Block copolymer having a weight average molecular weight of 5,000 to 1,000,000 and optionally terminated -NH ₂ -OH or -NCO.
-[(Alternate copolymer 1)-(Alternate copolymer 2)]-Formula (3)
The alternating copolymer 1 and the alternating copolymer 2 are bonded via a urea bond or a urethane bond.

In the block copolymer of the present invention, when both ends of alternating copolymer 1 are -NCO, both ends of alternating copolymer 2 are -NH ₂ or -OH; both of alternating copolymer 1 When the end is —NH ₂ , both ends of alternating copolymer 2 are —NCO. These two terminal groups undergo a polyaddition reaction to form a urea bond or a urethane bond to form the block copolymer of the present invention.

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

By changing the feed ratio (molar ratio) of the two monomers in the polyaddition reaction or polycondensation reaction, an alternating copolymer having an end group corresponding to the monomer structure can also be obtained, and the molecular weight is optionally determined. Can also be controlled. This is Billmeyer. F. W. Step-Reaction (Condensation) Polymerization. In Textbook of Polymer Science; John Wiley &Sons; Singapore, 1994; pp 35-39. It is described in.

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

For example, in the case of producing a copolymer in which both ends of alternating copolymer 1 are -NCO, diisocyanate compound <A> in the step of polyaddition of diisocyanate compound <A> and diamine compound <B> (step 1) The number of moles of H may be used relatively to the number of moles of diamine compound <B>. For example, when the number of moles of the diisocyanate compound <A> is n1 and the number of moles of the diamine compound <B> is n2, the respective numbers of moles satisfy the relationship of 1.06 ≦ n1 / n2 ≦ 1.9. It is preferable to adjust. In this way, the weight average molecular weight of the alternating copolymer 1 in which both ends are -NCO can be adjusted in the range of 500 to 300,000.

In such a case, since alternating copolymer 2 is produced with both ends of -NH ₂ or -OH, the diisocyanate compound <A> and the diamine compound <C ¹ > or the diol compound <C ² > In the step of polymerizing (step 2), the number of moles of diamine compound <C ¹ > or diol compound <C ² > may be increased relative to the number of moles of diisocyanate compound <A>. For example, assuming that the number of moles of the diisocyanate compound <A> is n1, and the number of moles of the diamine compound <C ¹ > or the diol compound <C ² > is n2, each mole number is 1.06 ≦ n2 / n1 ≦ 1. It is preferable to adjust so as to be in the relationship of .9. In this way, the weight average molecular weight of the alternating copolymer _{2 in} which both ends are -NH ₂ can be adjusted in the range of 500 to 300,000.

In addition, for example, in the case of producing a copolymer in which both ends of alternating copolymer 1 are -NH ₂ , a diamine compound is added in the step of polyaddition of diisocyanate compound <A> and diamine compound <B> (step 1) The number of moles of <B> may be increased relative to the number of moles of diisocyanate compound <A>. For example, assuming that the number of moles of the diisocyanate compound <A> is n1 and the number of moles of the diamine compound <B> is n2, the respective moles have a relationship of 1.06 ≦ n2 / n1 ≦ 1.9. It is preferable to adjust. In this way, the weight average molecular weight of the alternating copolymer 1 in which both ends are -NH ₂ can be adjusted in the range of 500 to 300,000.

In this case, since the alternating copolymer 2 having both ends of -NCO is to be produced, the step of polymerizing the diisocyanate compound <A> and the diamine compound <C ¹ > or the diol compound <C ² > In (Step 2), the number of moles of the diisocyanate compound <A> may be increased relative to the number of moles of the diamine compound <C ¹ > or the diol compound <C ² >. For example, assuming that the number of moles of the diisocyanate compound <A> is n1, and the number of moles of the diamine compound <C ¹ > or the diol compound <C ² > is n2, each mole number is 1.06 ≦ n1 / n2 ≦ 1. It is preferable to adjust so as to be in the relationship of .9. Thus, the weight average molecular weight of the alternating copolymer 2 in which both ends are -NCO can be adjusted to the range of 500 to 300,000.

Next, a method for producing a block copolymer will be described. The block copolymer is
(I) A method of producing a 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 a polyaddition reaction ( ii) A method of producing a block copolymer by introducing alternating copolymer 1 obtained in step 1 into a reaction vessel and then performing step 2 (iii) alternating copolymer weight obtained in step 2 Method for producing a block copolymer by introducing the united substance 2 into a reaction vessel and thereafter carrying out the step 1 (iv) After carrying out the step 1 in the same vessel, the block is subsequently carried out by carrying out the step 2 Method for producing copolymer (v) After carrying out step 2 in the same container, subsequently carrying out step 1 is a stepwise production method exemplified in the method for producing a block copolymer (steps below) Polymerization method is adopted. Although a block copolymer can be obtained in any step polymerization method, one or more step polymerization methods may be combined to obtain desired properties, or a plurality of selected step polymerization methods may be obtained. It is also possible to adopt a method of repeating the loop.

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

5 Other Diisocyanate Compounds <D>
The block copolymer of the present invention has both of the alternating copolymer 1 and the alternating copolymer 2 as a constituent unit of the diisocyanate compound <A>, that is, an aliphatic isocyanate structural unit (A) having a cyclic structure, but a diisocyanate You may replace and use a part of compound <A> by other diisocyanate compound <D> (structural unit (D)). The other diisocyanate compound may be contained in a part of alternating copolymer 1, may be contained in a part of alternating copolymer 2, and a part to which each alternating copolymer is bound Or may be bound to the end of the block copolymer.

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 the other diisocyanate compounds, the compounds shown below can be used.

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

Furthermore, as other diisocyanate compounds, for example, aliphatic diisocyanates, aromatic diisocyanates, sulfur-containing aliphatic diisocyanates, aliphatic sulfide diisocyanates, aromatic sulfide diisocyanates, aliphatic diisocyanates disclosed in JP-A-2016-199694 Examples thereof include sulfone type diisocyanates, aromatic sulfone type diisocyanates, sulfonic acid ester type diisocyanates, aromatic sulfonic acid amide type diisocyanates, sulfur-containing heterocyclic diisocyanates, and the like. As specific examples of these diisocyanate compounds, the following compounds may be mentioned.

The aromatic diisocyanate as used in the present invention is a compound having two isocyanate groups in the molecule, in which an isocyanate group is directly bonded to carbon of an aromatic ring. The 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 carbon of a heterocyclic ring containing a hetero atom.

Furthermore, the sulfide-based diisocyanate, the sulfone-based diisocyanate, the sulfonic acid ester-based diisocyanate, and the sulfonic acid amide-based diisocyanate of the present invention each have a structure of sulfide, sulfone, sulfonic acid ester, and sulfonic acid amide in the molecule, and It is a compound which has two isocyanate groups in the inside.

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-trimethylundecamethylene diisocyanate, 1,3,6-trimethylhexamethylene diisocyanate 1,8-Diisocyanate-4-isocyanatomethyloctane, 2,5,7-trimethyl-1,8-di Isocyanate-5-isocyanatomethyl octane, bis (isocyanatoethyl) mosquitoes - Boneto, bis (isocyanatoethyl) ether, 1,4-butylene glyco - distearate propyl ether omega, omega .'- diisocyanate, lysine diisocyanate methyl ester

Aromatic diisocyanates; xylylene diisocyanate (o-, m-, p-), tetrachloro-m-xylylene diisocyanate, 4-chloro-m-xylylene diisocyanate, 4,5-dichloro-m-xylylene diisocyanate, 2 1,3,5,6-Tetrabromo-p-xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, 4-ethyl-m-xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, 1 , 3-Bis (α, α-dimethylisocyanatomethyl) benzene, 1,4-bis (α, α-dimethylisocyanatomethyl) benzene, α, α, α ', α'-tetramethyl xylylene diisocyanate, bis (isocyanate Butyl) benzene, bis (a Sociate methyl) naphthalene, bis (isocyanato methyl) diphenyl ether, bis (isocyanato ethyl) phthalate, 2, 6 di (isocyanato methyl) furan, phenylene diisocyanate, tolylene diisocyanate, ethyl phenylene diisocyanate, isopropyl phenylene diisocyanate, dimethyl phenylene Diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, bibenzyl-4, 4'-diisocyanate Bis (isocyanatophenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, phenylisocyanate methylisocyanate, phenylisocyanate ethylisocyanate, tetrahydronaphthylene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4 ' -Diisocyanate, diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3-propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofuranisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate, Chloro carbazole diisocyanate

Sulfur-containing aliphatic diisocyanates; thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl 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 (isocyanatomethylthio) phenylmethane, bis (Isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) ethane, bis (isocyanatomethylthio) ethane, 1,5-i Cyanate 2-isocyanatomethyl-3- Chiapentan

Aliphatic sulfide diisocyanate; bis [2- (isocyanatomethylthio) ethyl] sulfide, bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanate methyl) sulfide ) Disulfide, bis (isocyanate ethyl) disulfide, bis (isocyanato propyl) disulfide

Aromatic sulfide diisocyanate; diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzyl thioether, bis (4-isocyanate methyl benzene) ) Sulfide, 4,4'-methoxybenzenethioethylene glycol-3,3'-diisocyanate, diphenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3 3,3'-Dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl disulfide-6,6'-diisocyanate, 4,4'-dimethyldiphenyl disulfide-5,5'-diisocyanate DOO, 3,3'-dimethoxy diphenyl disulfide-4,4'-diisocyanate, 4,4'-dimethoxy diphenyl disulfide-3,3'-diisocyanate

Aliphatic sulfone diisocyanate; bis (isocyanatomethyl) sulfone

Aromatic sulfone diisocyanate; diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzylidene sulfone-4,4'-diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate, 4-methyldiphenylmethane Sulfone-2,4'-diisocyanate, 4,4'-dimethoxydiphenyl sulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzyl sulfone, 4,4'-dimethyldiphenyl sulfone -3,3'-diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate, 4,4'-dimethoxybenzene ethylenedisulfone-3,3'-diisocyanate, 4,4'- Chloro-3,3'-diisocyanate

Sulfonic acid ester-based diisocyanate; 4-methyl-3-isocyanatobenzenesulfonyl-4'-isocyanate phenol ester, 4-methoxy-3-isocyanatobenzenesulfonyl-4'-isocyanate phenol ester

Aromatic sulfonic acid amide diisocyanate; 4-methyl-3-isocyanatobenzenesulfonylanilide-3'-methyl-4'-isocyanate, dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-dimethoxybenzenesulfonyl -Ethylenediamine-3,3'-diisocyanate, 4-methyl-3-isocyanatobenzenesulfonylanilide-4-methyl-3'-isocyanate

Sulfur-containing heterocyclic diisocyanates: thiophene-2,5-diisocyanate, thiophene-2,5-diisocyanate methyl, 1,4-dithiane-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanate methyl, 1,2 3-Dithiolane-4,5-diisocyanate, 1,3-dithiolane-4,5-diisocyanate methyl, 1,3-dithiolane-2-methyl-4,5-diisocyanate methyl, 1,3-dithiolane-2,2- Diethyl isocyanate, tetrahydrothiophene-2,5-diisocyanate, tetrahydrothiophene-2,5-diisocyanate methyl, tetrahydrothiophene-2,5-diisocyanate ethyl, tetrahydrothiophene-3,4-diisocyanate methyl, 2- (1,1-diisocyanate Trimethyl) thiophene, 3- (1,1-diisocyanatomethyl) thiophene, 2- (2-thienylthio) -1,2-diisocyanatopropane, 2- (3-thienylthio) -1,2-diisocyantepropane, 3- (2 -Thienyl) -1,5-diisocyanate-2,4-dithiapentane, 3- (3-thienyl) -1,5-diisocyanate-2,4-dithiapentane, 3- (2-thienylthio) -1,5-diisocyanate- 2,4-dithiapentane, 3- (3-thienylthio) -1,5-diisocyanate-2,4-dithiapentane, 3- (2-thienylthiomethyl) -1,5-diisocyanate-2,4-dithiapentane, 3- (3-thienylthiomethyl) -1,5-diisocyanate-2,4-dithiapentane, 2,5- ( Isocyanate methyl) thiophene, 2,3- (diisocyanatomethyl) thiophene, 2,4- (diisocyanatomethyl) thiophene, 3,4- (diisocyanatomethyl) thiophene, 2,5- (diisocyanatomethylthio) thiophene, 2,3- (di) Diisocyanatomethylthio) thiophene, 2,4- (diisocyanatomethylthio) thiophene, 3,4- (diisocyanatomethylthio) thiophene, 2,4-bisisocyanatomethyl-1,3,5-trithiane

In addition, although a diisocyanate compound is generally used to produce polyurea and polyurethane, it is industrially produced by reaction with phosgene using the corresponding diamine as a starting material. That is, the desired diisocyanate compound <A> and other diisocyanate compounds can also be produced from the diamine compound <B> as a starting material.

End groups of the block copolymer of the end groups present invention 6 block copolymer, but is either -NH 2 _-OH or -NCO, the end groups may be sealed. By sealing the end, storage stability of the block copolymer can be improved. For capping the end groups, end capping agents exemplified below can be used.

When the end group is -NCO, a compound having an -NH ₂ group, -OH group, -COOH group or -SO ₂ H group as an end capping agent can be used.

Specific examples of the compound having —NH ₂ group which can be used as an end capping agent include 1-aminobutane, 4-ethynylaniline, 3-ethynylaniline, propargylamine, 3-aminobutin, 4-aminobutin, 5-aminopentyne And 4-aminopentyne, allylamine, 7-aminoheptin, m-aminostyrene, p-aminostyrene, m-amino-α-methylstyrene, 3-aminophenylacetylene and 4-aminophenylacetylene. Among these, 1-aminobutane is preferable from the viewpoint of excellent reactivity. These monoamine compounds may be used alone or in combination of two or more.

Specific examples of the compound having an —OH group that can be used as an end capping agent include monoalcohol compounds having 1 to 18 carbon atoms. Examples of the monoalcohol compound having 1 to 18 carbon atoms include linear monools (methanol, ethanol, n-propanol, n-butanol, pentanol, hexanol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, Decyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol etc .; branched monool (isopropanol, sec-, iso- or tert-butanol, neopentyl alcohol, 3-methyl-pentanol and 2-ethylhexanol Etc .; monools having a cyclic group having 6 to 10 carbon atoms (alicyclic group-containing monools (eg, cyclohexanol etc.) and aromatic ring-containing monools (eg, benzyl alcohol) etc.). Furthermore, high molecular weight monools (polyester monools, polyether monools and polyether ester monools etc.), cellosolves and carbitols can be mentioned as specific examples of the compound having an —OH group.
Of these, linear monools are preferred. Specifically, methanol, ethanol, n-propanol, n-butanol and the like.
These monoalcohol compounds may be used alone or in combination of two or more.

When a compound having an —OH group is used as a terminal blocking agent, a general urethanization catalyst such as dibutyltin dilaurate can be used as a reaction catalyst. As the urethanization catalyst, for example, various nitrogen-containing compounds such as N, N-dimethylaminoethyl ether, triethylamine, triethylenediamine, or N-methylmorpholine, various salts such as potassium acetate, zinc stearate, or tin octylate Examples thereof include metal salts, various organic metal compounds such as dibutyltin dilaurate, and chelate compounds such as zirconium tetraacetylacetonate.

When the terminal reactive group is —NH _2, —OH, a compound having an —NCO group can be used as an end capping agent.

Specific examples of the compound having a -NCO group that can be used as the end capping agent include phenyl isocyanate, toluylene isocyanate, dimethyl phenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate and the like. 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 end capping agent, a general urethanization catalyst such as dibutyltin dilaurate can be used as a reaction catalyst. As the urethanization catalyst, for example, various nitrogen-containing compounds such as N, N-dimethylaminoethyl ether, triethylamine, triethylenediamine, or N-methylmorpholine, various salts such as potassium acetate, zinc stearate, or tin octylate Examples thereof include metal salts, various organic metal compounds such as dibutyltin dilaurate, and chelate compounds such as zirconium tetraacetylacetonate.

7 The solvent used for producing the reaction solvent alternating polymer 1, alternating polymer 2 and further the block copolymer of the present invention is not particularly limited as long as these copolymers can be synthesized. As the reaction solvent, for example, 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, 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, Tyl lactate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol 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- Toloxy-2-propanol), propylene glycol monomethyl ether (1-methoxy-2-propanol), triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl 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-acetyl- 2-Pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1, 3-Dimethy -2-imidazolidinone, γ-butyrolactone, 4-methyl-2-pentanone, methyl ethyl ketone, acetone, toluene, tetrahydrofuran, ethyl lactate, 3-methoxy N, N-dimethylpropanamide, isopropyl alcohol, normal butyl alcohol, normal propyl Alcohol, N, N-dimethylpropionamide, tetramethylurea, and dimethylsulfoxide can be mentioned.

Among these, propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, 4-methyl It is preferable to use -2-pentanone, N, N-dimethylpropionamide, tetramethylurea, or dimethylsulfoxide because the solubility of the polyurea alternating copolymer is good and the polymerization proceeds uniformly.
These reaction solvents may be used alone or in combination of two or more. Furthermore, other solvents may be mixed and used in addition to the above reaction solvents.

The reaction solvent is preferably used in an amount of 100 parts by weight or more based on 100 parts by weight in total of the diisocyanate compound <A> and the diamine compound <B> because the reaction proceeds smoothly. The reaction is preferably carried out at 0 ° C. to 150 ° C. for 0.2 to 20 hours.

8 Application of Block Copolymer The block copolymer of the present invention can be used as a material for protecting an image display element from impact in the image display element field represented by a liquid crystal display, an organic EL display, etc. . For example, in a liquid crystal display, a film or a coating material may be provided on the surface or the back surface of the cover glass or the cover film, or on the surface or the back surface of the polarizing plate. In the organic EL display, reduction in thickness and weight by flexibility has been advanced, and the need to protect the element from external force such as impact has become extremely high. Along with this, the block copolymer of the present invention is useful as a back film or coating material provided on the surface or back surface of a cover glass or cover film, the surface or back surface of a polarizing plate, or an element body. It can also be used as a material inside the element such as a filling material, a sealing material, a dam material, a buffer material, and a flattening film.

In the field of automobiles, it is also useful as a material for protecting the exterior and interior of automobiles from impact. For example, the outer coating may be a paint protection film or a coating material for protecting a scratch from stepping stones and the like. It is good also as a film and a coating material installed in an interlayer film, a glazing, a rear window, a rearview mirror, sensors, etc. of a laminated glass for motor vehicles taking advantage of the excellent shock absorption property of a block copolymer.

Polyurea and polyurethane-based materials also have the potential for use as biocompatible materials. It is also expected to be applied to medical devices that require blood compatibility such as filtering by filtration such as electrospinning to form dialysis membranes, hollow fibers such as artificial heart and lung, and needles for drips embedded for a long time in the body it can.

In the building materials field, it may be used as a film or a coating material to prevent the window glass of the high-rise building from being broken, scattered and dropped at the time of earthquake or earthquake disaster. It is also possible to prevent breakage of the glass. Polyurea is known to enhance impact resistance by coating it on structural buildings, such as concrete and block walls, and is also used as a coating material to prevent the collapse of structural buildings in terrorism, earthquakes, and earthquake disasters. Good.
The above-mentioned polyurea-based alternating copolymer can also be used in the same application as the block copolymer.

9 Resin Composition The resin composition of the present invention is a composition comprising the above block copolymer; and a solvent for dissolving the block copolymer.
The solvent used for 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 another solvent can be added and used as a mixed solvent.
In addition, after the block copolymer is isolated as a solid, it can be used by being redissolved in a desired solvent. As a method of isolating the block copolymer, a solution containing the block copolymer and the reaction solvent is poured into a poor solvent for the block copolymer such as methanol, ethanol, isopropyl ether to precipitate the block copolymer. And separation by filtration, washing, drying and the like. By such an operation, removal of the catalyst used for the production of the block copolymer can also be achieved.
Particularly preferred solvents are propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, 4 Mention may be made of -methyl-2-pentanone, N, N-dimethylpropionamide, tetramethylurea, dimethyl sulfoxide. These solvents may be used alone or in combination of two or more. It is preferable to use these solvents because the deposition of a polymer can be prevented at the time of film production, and a transparent and flat film can be produced.

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

The resin composition of the present invention may further contain additives such as a UV absorber and a light stabilizer (HALS).

Examples of the UV absorber include benzotriazoles, hydroxyphenyl triazines, benzophenones, salicylates, cyanoacrylates, triazines, and dibenzoylresorcinols. These ultraviolet absorbers may be used alone, or a plurality of ultraviolet absorbers may be used in combination. It is preferable that the type and combination of the ultraviolet absorber be appropriately selected based on the wavelength of ultraviolet light to be absorbed.

As UV absorbers, Adekastab LA-46, Adekastab LA-77Y, Adekastab LA-63P, Adekastab LA-72, Adekastab LA-32, Adukastab LA-32 manufactured by ADEKA Co., Ltd., Tinubin 479 manufactured by BASF, Tinuvin 292, Tinuvin 123, Tinuvin 384-2, tinuvin 400, and the like.

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

As a light stabilizer (HALS), TINUVIN (registered trademark) 5100 (general-purpose HALS of neutral type) manufactured by BASF, TINUVIN 292 (compound name: bis (1,2,2,6,6-pentamethyl-4-piperidinyl) Sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), TINUVIN 152 (compound name: 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2 6,6-Tetramethylpiperidin-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] butyl Malonate), TINUVIN 123 (compound name: decanedioic acid, reaction product of bis (2,2,6,6-tetramethyl-1- (octyloxy) -4 piperidinyl) ester (1,1-dimethylethyl hydroperoxide) And octane), TINUVIN 111 FDL (about 50%, TINUVIN 622, compound name: (butanedioic acid polymer (4-hydroxy-2,2,6,6-tetramethyl piperidinyl-yl) ethanol), about 50% , CHIMAS SORB 119, compound name: N-N'-N ''-N '' '-tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) ) Amino) triazine -2- yl)-4, 7- diazadecane-1, 10- diamine) or stock company Adeka Stub LA series, etc. made by Adeka, specifically, LA-52 ((5) -6116), LA-57 ((5) -5555), LA-62 ((5) -5711), LA-67 (( 5) -5755) can be mentioned. The numbers in parentheses are the existing chemical substance numbers specified in the Act on the Examination of Chemical Substances in Japan and the Regulation on Production etc.

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

In addition, as necessary, active energy ray sensitizers, polymerization inhibitors, waxes, plasticizers, leveling agents, surfactants, dispersants, antifoaming agents, wettability improvers, antistatic agents, curing assistants, Various additives such as additives imparting anti-soiling properties and low friction characteristics, additives imparting scratch resistance, heat stabilizers, flame retardants, mold release agents can be mixed.

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 a general-purpose organic solvent and has good heat resistance and mechanical properties.
The resin composition of the present invention may be a composition containing the above-mentioned polyurea alternating copolymer and a solvent for dissolving the above polyurea alternating copolymer.

10 Coating Film The coating film of the present invention can be obtained by removing the solvent after forming the resin composition of the present invention on a supporting substrate or a structure by a method such as coating, printing, casting or the like. The removal method may be, for example, drying, and the drying method is not particularly limited. Heating (hot air) drying, vacuum drying, steam drying, barrel drying, spin drying, suction drying and the like can be mentioned.
The drying method or drying conditions may be appropriately selected depending on the type of solvent of the resin composition, the thickness and shape of the coating film, and the like. For example, in the case of heat drying, a heat treatment using an air circulating constant temperature oven, a heater using microwave or far infrared rays, a hot plate or the like can be mentioned. The drying conditions are not particularly limited as long as the solvent evaporates, but, for example, the drying temperature may be 40 to 250 ° C., and the drying time may be 1 minute to 24 hours. The heating may be performed in two steps, and as necessary, the heating and drying may be performed under a nitrogen atmosphere or under reduced pressure.
The coating film from which the solvent has been removed may be determined in accordance with the application described in the above-mentioned "application of block copolymer". Alternatively, the solvent may be distilled off after the resin composition is applied to the target portion.
Such a configuration is preferable because a flat coating film is obtained.

11 Resin Film The resin film of the present invention is a film in which the solid content obtained by removing the solvent from the resin composition of the present invention is formed. For example, it can be produced by the steps of application, drying and peeling of the resin composition. The resin film may be used as a single layer, or may be used as a film in which a plurality of layers are laminated by repeating application and drying.
It is preferable to laminate a plurality of layers because the combination of resin films having different strengths can further enhance shock absorption.

In the case of a single layer, the thickness of the film is preferably 10 to 1000 μm, more preferably 20 to 500 μm, and particularly preferably 30 to 400 μm. A thickness of 30 μm or more is preferable because a film can be easily obtained, and a thickness of 400 μm or less is preferable because the product can be thinned.
In the case of two layers, the thickness of each film is preferably at least 1 to 999 μm, more preferably 10 to 490 μm, and particularly preferably 10 to 390 μm. When it is 10 μm or more, it is preferable because it is easily obtained as a film, and when it is 390 μm or less, it is preferable because the product can be thinned.
In the case of three layers, the thickness of each film is preferably at least 1 to 998 μm, more preferably 10 to 480 μm, and particularly preferably 10 to 380 μm. When it is 10 μm or more, it is preferable because it is easily obtained as a film, and when it is 380 μm or less, it is preferable because the product can be thinned.
In the case of a plurality of layers, the total thickness of the resin film is preferably 10 to 1000 μm, more preferably 20 to 500 μm, and particularly preferably 30 to 400 μm. A thickness of 30 μm or more is preferable because a film can be easily obtained, and a thickness of 400 μm or less is preferable because the product can be thinned.

The formation of the resin film is not particularly limited as long as it can produce a thin film. A wet coating method (application method) other than the method using the applicator used in the examples may be used. By using the coating method, excellent surface smoothness can be obtained. Among the coating methods, spin coating method and bar coating method can be exemplified in which a simple and uniform film formation is possible when a small amount is prepared. In the case of roll-to-roll where productivity is important, the gravure coating method, die coating method, reverse coating method, roll coating method, slit coating method, dipping method, spray coating method, kiss coating method, reverse kiss coating method, air A knife coat method, a curtain coat method, a rod coat method, an inkjet method etc. can be mentioned. Further, methods using various printing apparatuses such as a letterpress printing method, an intaglio printing method, a lithographic printing method, and a stencil printing method can be mentioned. It may be suitably selected according to the required thickness, viscosity, curing conditions, etc. from among these methods.

12 OLED Device The OLED device of the present invention comprises the resin film of the present invention. The OLED device may be either rigid or flexible. Because of the excellent flexibility of the resin film, it is more suitable for flexible type devices.
Furthermore, since the resin film of the present invention has excellent transparency and heat resistance, it is used as a transparent substrate in place of the conventional glass substrate and polyethylene naphthalate (PEN) film substrate in a bottom emission type flexible OLED element be able to. Alternatively, it can be laminated on or under a conventional substrate and used as an impact absorbing film.
In the top emission type flexible OLED element, it can replace with sealing glass and can use as a sealing film. Alternatively, it may be laminated on conventional sealing glass or under sealing glass and used as an impact absorbing film. Alternatively, it can be used as a transparent substrate in place of the conventional glass substrate, polyimide (PI) film substrate and polyethylene naphthalate (PEN) substrate.
Ordinary polyurea resin is excellent in properties such as heat resistance and mechanical strength, but its use form is limited because the reactivity between the isocyanate component and the amine component is high and the cured product is insoluble in general-purpose organic solvents. It is difficult to apply to the field of electronic information materials where precise coating is required.
However, since it became possible to synthesize a polyurea resin soluble in a general-purpose organic solvent according to the present invention, the resin composition can be applied and dried to a desired place, and the application to the electronic information field is possible. It has become possible.
The OLED device of the present invention can prevent breakage of the OLED device because it is provided with a shock absorbing layer.

13 Light Emitting Device The light emitting device of the present invention comprises the OLED element of the present invention. As a light emitting device, an organic EL display, particularly a flexible organic EL display, an organic EL illumination, particularly a flexible organic EL illumination can be mentioned.
The organic EL display is not particularly limited as long as it comprises the OLED element of the present invention. For example, a television, a portable information terminal, a wearable system, an in-vehicle display, digital signage, etc. can be mentioned.
According to the present invention, since the shock absorbing layer is provided, the failure of the light emitting device due to the breakage of the OLED element can be prevented.

Hereinafter, the present invention will be more 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 (manufactured by Wakayama Seika Kogyo Co., Ltd.)
DMAc: N, N-dimethylacetamide (Kanto Chemical Co., Ltd., dehydrated)
THF: tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph)
DMF: N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph)
DEF: N, N-diethylformamide (made by Tokyo Chemical Industry Co., Ltd.)
HXDI: 1,3-bis (isocyanate methyl) cyclohexane (manufactured by Mitsui Chemicals, Inc., product name; Takenate 600)
Solmix AP-1: ethanol, 2-propanol, methanol, water mixture (made by Nippon Alcohol Sales)
Silaplain FM 4411: Both terminal hydroxyl modified silicon compound, hydroxyl equivalent: 564 g / mol (manufactured by JNC Co., Ltd.)
Silaprene FM 3311: α, ω- (3-aminopropyl) polydimethylsiloxane (manufactured by JNC Co., Ltd.)
Organics ZC-150: zirconium tetraacetylacetonate (made by Matsumoto Fine Chemical Co., Ltd.)
Mw: weight average molecular weight PDI (Mw / Mn): molecular weight distribution index

Next, analysis conditions in Production Examples and Examples are shown.
<GPC>
Device: LC-2000 Plus series (detector: differential refractometer) manufactured by JASCO Corporation
Solvent: THF / DMF = 1/1 (v / v)
Flow rate: 0.5 ml / min
Column temperature: 40 ° C
Column used: Showa Denko KK Asahipak GF-1G 7B (guard column) + Asahipak GF-7M HQ, exclusion limit molecular weight (PEG) = 10,000,000
Calibration curve standard: PSt

1 block copolymer [Production example 1] Synthesis of alternating copolymer (1) BAPP (14.3 g), DMAc (b) in a 200 mL three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. Introduced 57.4g). It was heated to 120 ° C. using an oil bath. Next, a solution of HXDI (5.66 g) dissolved in DMAc (22.6 g) was introduced at once by a syringe to start the reaction (HXDI: BAPP = 1.0: 1.2, molar ratio). Then, while maintaining at 120 ° C., stirring was carried out for 6 hours to obtain a clear reaction liquid. Mw calculated | required by GPC analysis of the reaction liquid was 8,200, and 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 dropped using a Pasteur while stirring with a stirrer. A white solid precipitated in the solution. The precipitates were collected by suction filtration, and then dried for 6 hours in a vacuum dryer set at 120 ° C. to obtain the desired alternating copolymer (1).

Preparation Example 2 Synthesis of Alternating Copolymer (2) HXDI (51.1 g), DMAc (249.0 g) in a 1,000 mL three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. Introduced. While the flask was immersed in a water bath and a cooled state was maintained, a solution in which Silaprene FM 4411 (198.8 g) was dissolved was added dropwise using a dropping funnel to start the reaction (HXDI: FM 4411 = 1.5: 1, molar ratio). Then, the reaction was continued for 6 hours to obtain a clear reaction solution. Mw calculated | required by GPC analysis of the reaction liquid is 6,100, PDI is 1.9, The target alternating copolymer (2) was obtained.

[Preparation Example 3] Synthesis of alternating copolymer (3) HXDI (4.26 g) and DMAc (57.6 g) were introduced into a 200 mL three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. did. Thereafter, it was heated at 40 ° C. using an oil bath. A solution in which DMAc (14.4 g) was added to and dissolved in FM 3311 (13.74 g) was added dropwise to initiate a reaction (HXDI: FM3311 = 1.5: 1, molar ratio). Then, it stirred at the same temperature for 5 hours, and obtained the clear reaction liquid. Mw calculated | required by GPC analysis of the reaction liquid is 9,900, PDI is 3.2, and obtained the target alternating copolymer (3).

Preparation Example 4 Synthesis of Alternating Copolymer (4) DMAc (750.6 g) was introduced into the alternating copolymer (2) synthesized in Preparation Example 2 to adjust its concentration to 20%. Furthermore, methanol (8.4 g) is introduced, and the terminal isocyanate group of alternating copolymer (2) is reacted with methanol by stirring for 30 minutes to inactivate to obtain alternating copolymer (4). The

Preparation Example 5 Synthesis of Alternating Copolymer (5) Methanol (0.7 g) is introduced into a reaction solution obtained by heating the alternating copolymer (3) synthesized in [Preparation example 3] to 40 ° C. The terminal isocyanate group of the alternating copolymer (3) was reacted with methanol by stirring for a minute to inactivate the resin, thereby obtaining an alternating copolymer (5).

Example 1 Synthesis of Block Copolymer (1) The alternating copolymer obtained in [Preparation Example 1] in a three-necked flask (200 mL) equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. 1) (5.02 g) was introduced and then DMAc (20.0 g) was added. After heating to 120 ° C. using an oil bath, the alternating copolymer (2) (30.0 g) obtained in [Production Example 2] and DMAc (45.1 g) were introduced into the dropping funnel ( Copolymer concentration: 20%). After that, dropping was rapidly started, and the alternating copolymer (1) and the alternating copolymer (2) were uniformly mixed in the flask while being stirred (alternating copolymer (1): alternating copolymer (2) ) = 1: 3, weight ratio). The block copolymer (1) was obtained by stirring and reacting at the same temperature for 6 hours. The resulting reaction solution was clear, and the Mw determined by GPC analysis was 61,000, and the PDI was 6.0.

[Example 2] Synthesis of block copolymer (2) Alternating copolymer obtained in [Preparation Example 3] in a three-necked flask (200 mL) equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. (3) (75.0 g) was introduced. It was then heated to 120 ° C. using an oil bath. A solution obtained by mixing 5.00 g of the alternating copolymer (1) obtained in [Preparation Example 1] and DMAc (20.0 g) was introduced into the dropping funnel (copolymer concentration: 20%). After that, dropping was rapidly started, and the alternating copolymer (1) and the alternating copolymer (3) were uniformly mixed in the flask while being stirred (alternating copolymer (1): alternating copolymer (3) ) = 1: 3, weight ratio). The block copolymer (2) was obtained by stirring and reacting at the same temperature for 6 hours. The resulting reaction solution was clear, and the Mw determined by GPC analysis was 132,000, and the PDI was 15.9.

[Example 3]
The reaction solution containing 1.0 g of the block copolymer (1) synthesized in [Example 1] was coated on an aluminum substrate and heated on a hot plate heated to 120 ° C. for 1 hour to remove the solvent and remove the solvent. A homogeneous membrane (1) was obtained. As a result of peeling the film (1) from the aluminum substrate, it was possible to obtain a transparent and homogeneous free standing film.

Example 4
The reaction liquid containing 1.0 g of the 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 distill the solvent away. A homogeneous membrane (2) was obtained. As a result of peeling the film (2) from the aluminum substrate, it was possible to obtain a transparent and homogeneous free standing film.

Comparative Example 1 Preparation of Film (3) in which Alternating Copolymer (1) and Alternating Copolymer (4) are Mixed The alternating copolymer (1) synthesized in [Preparation Example 1] was treated with 1.00 g of DMAc4. 02 g was added to prepare a solution with a solid concentration of 20 wt%. Further, a 20 wt% solution of alternating copolymer (1) and the alternating copolymer (4) synthesized in [Production Example 4] are prepared as alternating copolymer (1): alternating copolymer (4) = 1: 3. It mixed so that it might become (weight ratio). The mixture was a cloudy and inhomogeneous solution.
The mixed solution (1.00 g) was applied to an aluminum base and heated on a hot plate heated to 120 ° C. for 1 hour to distill off the solvent, whereby a white turbid film (3) was obtained. As a result of peeling the film (3) from the aluminum substrate, it was not possible to obtain a free standing film.

Comparative Example 2 Preparation of Film (4) in which Alternating Copolymer (1) and Alternating Copolymer (5) are Mixed The alternating copolymer (1) synthesized in [Preparation Example 1] was treated with 1.00 g of DMAc4. 02 g was added to prepare a solution with a solid concentration of 20 wt%. Further, a 20 wt% solution of alternating copolymer (1) and the alternating copolymer (5) synthesized in [Preparation Example 5] were prepared by using alternating copolymer (1): alternating copolymer (5) = 1: 3. It mixed so that it might become (weight ratio). The mixture was a cloudy and inhomogeneous solution.
The mixed solution (1.00 g) was applied to an aluminum substrate and heated on a hot plate heated to 120 ° C. for 1 hour to distill off the solvent, whereby a cloudy film (4) was obtained. As a result of peeling the film (4) from the aluminum substrate, it was not possible to obtain a free standing film.

 

 

From Table 1, it can be seen that Example 3 and Example 4 and Comparative Examples 1 and 2 are clearly different, and it is understood that the target block copolymer is obtained.

2 Synthesis of Polymer (11) as Resin Film [Production Example 11] Alternating Copolymer
Under a nitrogen atmosphere, BAPP (4.06 g) was placed in a 100 ml three-necked flask fitted with a reflux condenser and a thermometer, DEF (17 ml) was added, and dissolved using a stirrer. It was heated to 120 ° C. using an oil bath. After that, a solution of HXDI (1.94 g) dissolved in DEF (5.3 ml), which had been previously prepared in a 30 ml sample bottle, was added using a funnel (BAPP: HXDI = 1: 1.01, molar ratio). The HXDI DEF solution remaining in the 30 ml sample bottle was washed with DEF (2.9 ml) and added to the reaction solution. Then, the reaction was carried out for 4 hours while maintaining at 120 ° C., followed by cooling with a water bath, and 1 ml of methanol was added to quench the excess isocyanate group. Mw calculated by GPC analysis of the reaction liquid was 126,000, PDI was 20.0, and the polymer (11) which is a polyurea polymer containing a structural unit of the target alternating copolymer was obtained.

Preparation Example 12 Synthesis of Polymer (12) as Alternating Copolymer
HXDI (2.7 g) and DMAc (50.1 g) were introduced into a 200 mL three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. While keeping the flask immersed in a water bath and maintaining the cooled state, Silaprene FM3311 (12.3 g) was added dropwise over 5 minutes using a dropping funnel (HXDI: FM3311 = 1.06: 1, molar ratio). Furthermore, FM3311 attached to the dropping funnel was introduced into the flush flask using a DMAc (10.0 g). The reaction was then continued for 2 hours to obtain a clear reaction solution. Mw calculated | required by GPC analysis of the reaction liquid was 34,000, PDI was 7.0, and obtained the polymer (12) which is a polyurea type polymer containing the structural unit of the target alternating copolymer.

Preparation Example 13 Synthesis of Polymer (13) as Block Copolymer
Synthesis of alternating copolymer 1 represented by formula (1):
BAPP (71.7 g) and DMAc (287.0 g) were introduced into a 1000 mL three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. It was heated to 120 ° C. using an oil bath. Next, a solution of HXDI (28.3 g) dissolved in DMAc (113.8. G) was introduced into the dropping funnel and dropped into the flask to start the reaction (HXDI: BAPP = 1.0: 1.2 , Molar ratio). Then, while maintaining at 120 ° C., stirring was performed for 5 hours to obtain a clear reaction solution. The Mw determined by GPC analysis of the reaction solution was 17,000, and the PDI was 3.5.
Furthermore, a mixed solution of Solmix AP-1 (2160 mL) and acetone (240 ml) was prepared in a 3 L beaker, and the obtained polymerization solution (82 g) was slowly dropped using a Pasteur while stirring with a stirrer. A white solid precipitated in the solution. The precipitate was recovered by suction filtration. The same operation was performed four times to obtain a white solid containing a solvent. The obtained white solid was dried in a vacuum drier set at 120 ° C. for 6 hours to obtain 59 g of the target alternating copolymer 1 represented by the formula (1).

Synthesis of alternating copolymer 2 represented by formula (2-1):
In a nitrogen atmosphere, HXDI (23.7 g) and DMAc (310.2 g) were introduced into a 1000 mL three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel. Thereafter, it was heated at 40 ° C. using an oil bath. A solution in which DMAc (80.2 g) was added to and dissolved in FM3311 (73.3 g) was added dropwise to initiate a reaction (HXDI: FM3311 = 1.5: 1, molar ratio). Then, it stirred at the same temperature for 6 hours, and obtained the clear reaction liquid. Mw calculated | required by GPC analysis of the reaction liquid is 11,000, PDI is 4.0, and obtained the reaction liquid of alternating copolymer 2 represented by Formula (2-1) made into the objective.

Synthesis of block copolymer:
The reaction solution (375.0 g) of the alternating copolymer 2 represented by the formula (2-1) was introduced into a three-necked flask (1000 mL) equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. It was then heated to 120 ° C. using an oil bath. A solution obtained by mixing 24.9 g of the alternating copolymer 1 represented by the formula (1) and DMAc (119.5 g) was introduced into the dropping funnel (copolymer concentration: 19%). After that, the dropping was rapidly started, and the alternating copolymer 1 and the alternating copolymer 2 were uniformly mixed and reacted in a flask while being stirred (alternating copolymer 1: alternating copolymer 2 = 1: 3, Weight ratio). The mixture was stirred at the same temperature for 5 hours to obtain a target block copolymer (13). The resulting reaction solution was clear, and the Mw determined by GPC analysis was 98,000, and the PDI was 9.3.

Production Example 14 to Production Example 17 Synthesis of Polymer (14) to Polymer (17)
Polymers which are block copolymers different in molecular weight by the method according to [Production Example 13] except that the composition such as the molar ratio and the weight ratio, and that methanol is added and quenched in the course of the reaction of the block copolymer. ) To polymer (17) were synthesized.

Production Example 18 to Production Example 20 Synthesis of Polymer (18) to Polymer (20)
After changing FM3311 to FM4411 and adding 0.5 wt% of Orgatics ZC-150 as a catalyst to the total weight of HXDI and FM4411, the reaction at 80 ° C. Except having obtained the reaction liquid of alternating copolymer 2 represented by -2), polymers (18) to polymers ((1) to (2) having different molecular weights by the method according to [Production Example 14] to [Production Example 17] 20) was synthesized.

Preparation 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.

Preparation Example 22 Synthesis of Polymer (22)
The target block copolymer weight is the method according to Production Example 19 except that the molar ratio, the reaction scale, and the reaction temperature of the alternating copolymer 2 represented by the formula (2-2) are 25 ° C. The combined polymer (22) was synthesized.

  The compositions, Mw and PDI of the polymers (11) to (22) obtained are shown in Table 2.

Example 11 Production of Resin Film (11) A release film (product name: NSD-100, 100 μm, manufactured by Fujimori Kogyo Co., Ltd.) was used as a substrate. The polymer (11) (concentration: 19%, solvent: DEF) synthesized in Production Example 11 is cast on a substrate, and a Baker type film applicator (Product name: No. 510 Baker type film applicator, manufactured by Yasuda Seiki Co., Ltd.) The coating thickness of a uniform film thickness was produced by adjusting the scale of the both sides of) and adjusting the gap distance of an applicator and a base material. After drying at 120 ° C. for 15 minutes, the release film was removed to obtain a single-layer resin film (11) with a film thickness of 40 μm.

[Example 12] to [Example 20] Preparation of resin film (12) to resin film (20)
A single-layer resin film (a polymer film (12) to a polymer (20) were used instead of the polymer (11), and the method according to Example 11 was used except that the scale, concentration and solvent of the applicator were changed. 12) to a resin film (20) were obtained.

  Table 3 shows the properties and film thickness of the single-layered resin film obtained.

Comparative Example 11
The transparent polyimide (film thickness: 50 μm) was also subjected to the following test.
Comparative Example 12
Also in the case where the resin film was not placed, it was similarly subjected to the following test.

<Shock absorption test>
A chrome steel ball (model number: CR-3 / 4, material: chrome steel (SUJ-2), size: 3/4 inch, manufactured by As One Co., Ltd.) was dropped from a height of 10 cm. The resin film sample was placed at the dropping point, and SUS430 (0.5 cm in thickness) was placed under it. A general-purpose piezoelectric load cell (model: 208C05, manufactured by PCB Piezotronics) is installed under SUS 430, and the impact force applied to the resin film sample when dropped is measured using an oscilloscope (model: DS-5107B, manufactured by Iwasaki Communication Co., Ltd.) Measured. A signal conditioner (model: 480C02, manufactured by PCB Piezotronics) was connected between the general-purpose piezoelectric load cell and the oscilloscope.
In addition, as for the resin film sample, slide glass (Product name: ASLAB, MICROSCOPE SLIDES, 25 mm × 75 mm, thickness: 1 mm, manufactured by As One Corp.) to a length of about 25 mm × 30 mm and cut the resin film on or under the glass The ones that I put were prepared respectively.

<Glass protection test>
The state of the glass after the impact absorption test was observed.
In the case where the glass is broken, it is considered that measurement is impossible in the impact absorption test because it is considered that a part of the impact force contributes to the glass breakage.

 

  The results of the impact absorption test and the glass protection test in the case of only the single-layer resin film of Example 11 to Example 20, the single-layer transparent polyimide of Comparative Example 11, and the glass of Comparative Example 12 are shown below.

Test results:
According to Tables 4 and 5, although the glass alone breaks the glass by falling balls, it protects the glass not only when the resin film of Examples 11 to 20 is put on the glass but also when the film is put under it. It became clear that there was a function to
In addition, the transparent polyimide protects the glass more than the resin films of Examples 11 to 20 because the glass is broken when the film is placed on the glass, but is not broken when the film is placed under the glass. It turned out that the function is small.

[Example 21] Preparation of laminated resin film (21) consisting of polymer (21) / polymer (22) / polymer (21)
Formation of resin layer 11:
The polymer (21) (the concentration: 20%, the solvent: DMAc) containing the alternating copolymer 2 of the formula (2-1) synthesized in Production Example 21 was distilled of the solvent under reduced pressure to give a concentration of 42%. The prepared solution was used in advance. A release film was used as a substrate. A polymer (21) (42% concentration) was cast on a substrate, and a coating film of uniform film thickness was produced using a variable-type baker film applicator (model: 3530/6, manufactured by Elcometer Corporation). After drying at 120 ° C. for 15 minutes, a resin layer 11 having a thickness of 35 μm was obtained.

Formation of resin layer 12:
Furthermore, the polymer (22) (concentration: 20%, solvent: DMAc), which was synthesized in Production Example 22 and contains the alternating copolymer 2 of the formula (2-2), was evaporated under reduced pressure to remove the solvent, and the concentration was 46%. The solution was applied onto the resin layer 11 and a coated film having a uniform film thickness was produced using an applicator (product name: No. 510 Baker type film applicator, manufactured by Yasuda Seiki Co., Ltd.). After drying at 120 ° C. for 15 minutes, a resin layer 12 which is a two-layer film (total film thickness: 65 μm) consisting of polymer (21) / polymer (22) was obtained.

Formation of resin layer 13: Preparation of laminated resin film (21) Furthermore, a polymer (21) (42% concentration) was cast on the resin layer 12 and an applicator (product name: No. 510 Baker type film applicator, (stock A coating film of uniform film thickness was produced using Yasuda Seiki Co., Ltd.). After drying at 120 ° C. for 15 minutes, a resin layer 13 is obtained which is a three-layer film (total film thickness: 100 μm) consisting of polymer (21) / polymer (22) / polymer (21). The release film was removed to obtain a laminated resin film (21).

[Example 22] Preparation of laminated resin film (22) consisting of polymer (22) / polymer (21) / polymer (22)
Formation of resin layer 14:
The polymer (22) (the concentration: 20%, the solvent: DMAc) containing the alternating copolymer 2 of the formula (2-2) synthesized in Production Example 22 is distilled of the solvent under reduced pressure to give a concentration of 46%. The prepared solution was used in advance. A release film was used as a substrate. The polymer (22) (concentration 46%) was cast on a substrate, and a coating film having a uniform film thickness was produced using a variable-type baker film applicator (model: 3530/6, manufactured by Elcometer Corporation). After drying at 120 ° C. for 15 minutes, a resin layer 14 with a thickness of 35 μm was obtained.

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

Formation of resin layer 16: Preparation of laminated resin film (22) Furthermore, the polymer (22) (concentration: 20%, solvent: DMAc) synthesized in Production Example 22 was evaporated under reduced pressure to remove the solvent, and the concentration was 46%. The solution was applied onto the resin layer 15 and a coated film having a uniform film thickness was produced using an applicator (product name: No. 510 Baker type film applicator, manufactured by Yasuda Seiki Co., Ltd.). After drying at 120 ° C. for 15 minutes, a resin layer 16 which is a three-layer film (total film thickness: 100 μm) consisting of polymer (22) / polymer (21) / polymer (22) was obtained. The release film was removed to obtain 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 treated with a solvent under reduced pressure. The solution was evaporated in advance to a concentration of 50% and used. A release film was used as a substrate. A polymer (21) (50% concentration) was cast on a substrate, and a coating film of uniform film thickness was produced using an applicator (product name: No. 510 Baker type film applicator, manufactured by Yasuda Seiki Co., Ltd.) . After drying at 120 ° C. for 15 minutes, the release film was removed to obtain a single-layer resin film (23) with a film thickness of 100 μm.

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

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

[Example 26] Preparation of resin film (26) of lamination using polymer (22) A method according to Example 25 except that polymer (22) was used instead of polymer (21), A laminated resin film (26) having a total film thickness of 400 μm was obtained.

  Table 6 shows the properties and film thicknesses of the laminated and single-layered resin films obtained.

Comparative Example 13
Two sheets of transparent polyimide (film thickness: 50 μm) were stacked (total film thickness: 100 μm) and subjected to the following test.
Comparative Example 14
Eight transparent polyimides (film thickness: 50 μm) were stacked (total film thickness: 400 μm) and subjected to the following test.

<Shock absorption test>
An impact absorption test was conducted under the same conditions as in Example 11 to Example 20 except that the chrome steel ball was dropped from a height of 30 cm, and that the glass was removed from the resin film sample to avoid the influence of glass breakage. .
<Glass protection test>
The protection of the glass was carried out by the method according to Example 11 to Example 20 except that a resin film was placed on a SUS vat, under a glass, and a chrome ball was dropped using a 50 cm high acrylic pipe. It was tested.

  The results of impact absorption test and glass protection test of the laminated or single layer resin film (film thickness 100 μm) of Example 21 to 24 and the transparent polyimide (film thickness 100 μm) of Comparative Example 13 are shown below.

Test results:
In each of Examples 21 to 24, the impact force was smaller than that of Comparative Example 13. Moreover, the laminated film of Example 21 had the smallest impact force.

The results of an impact absorption test of the laminated resin films (film thickness 400 μm) of Example 25 and Example 26 and the transparent polyimide (film thickness 400 μm) of Comparative Example 14 are shown below.

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

All documents, including publications, patent applications and patents cited in the present specification, are specifically indicated individually for each document, and are incorporated by reference, and the entire contents thereof are described herein. To the same extent, incorporated herein by reference.

The use of nouns and similar designations used in connection with the description of the invention (in particular in connection with the following claims) is not specifically pointed out herein, or unless it is clearly inconsistent with the context , Both singular and plural. The terms "comprising", "having", "including" and "including" are to be construed as open end terms (ie meaning "including but not limited to") unless otherwise indicated. The recitation of numerical ranges herein is merely intended to serve as a shorthand method of referring individually to each value falling within the range, unless otherwise indicated herein. And each value is incorporated into the specification as if individually listed herein. All methods described herein may be performed in any suitable order, unless otherwise indicated herein or otherwise obviously inconsistent with the context. Unless otherwise stated, all examples or exemplary phrases (e.g. "such as") used herein are merely intended to better illustrate the invention and provide a limitation on the scope of the invention. is not. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

Preferred embodiments of the invention are described herein, including the best mode known to the inventors for carrying out the invention. Modifications of these preferred embodiments will be apparent to one of ordinary skill in the art upon reading the above description. The inventors expect skilled artisans to apply such variations as appropriate, and intend to practice the present invention in ways other than those specifically described herein. . Accordingly, the present invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Furthermore, any combination of the above-described elements in all variations is also encompassed within the invention, unless otherwise specifically indicated herein or otherwise obviously inconsistent with the context.

The block copolymer of the present invention is useful not only as a base resin for coating materials and film substrates, but also has amino groups and isocyanate groups at both ends and also has urethane and urea bonds in the main chain. It is also very useful as a reactive oligomer.

Claims (16)

A repeating unit represented by the formula (3), which is a polyaddition copolymer of the following alternating copolymer 1 and the following alternating copolymer 2, having a weight average molecular weight of 5,000 to 1,000,000, Is either -NH ₂ -OH or -NCO which may be end-capped,
Block copolymer.
-[(Alternate copolymer 1)-(Alternate copolymer 2)]-Formula (3)
Alternating copolymer 1:
A polyaddition copolymer of a diisocyanate compound <A> and a diamine compound <B>, which is represented by the formula (1)
-[(A)-(B)]-Formula (1)
A polyurea-based alternating copolymer containing a repeating unit represented by the following formula, having a weight average molecular weight of 500 to 300,000, and having both ends of -NH ₂ or -NCO;
Alternating copolymer 2:
A polyaddition copolymer of a diisocyanate compound <A> and a diamine compound <C ¹ >, which is represented by the formula (2-1)
-[(A)-(C ¹ )]-Formula (2-1)
And a polyurea-based alternating copolymer 2-1 having a weight average molecular weight of 500 to 300,000 and having both ends of -NCO or -NH ₂ .
And a polyaddition copolymer of a diisocyanate compound <A> and a diol compound <C ² >, which is represented by the formula (2-2)
-[(A)-(C ² )]-Formula (2-2)
And a polyurethane-based alternating copolymer 2-2 having a weight average molecular weight of 500 to 300,000 and having -NCO or -OH at both ends.
At least one alternating copolymer selected from:
(Wherein (A) is each independently at least one kind of aliphatic isocyanate structural unit having a cyclic structure in the molecule;
(B) each independently represents at least one structural unit selected from an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton;
(C ¹ ) represents at least one structural unit selected from linear aliphatic diamines, aliphatic diamines having an ether bond, and diamines having a siloxane skeleton;
(C ² ) represents at least one structural unit selected from linear aliphatic diols, aliphatic diols having an ether bond, and diols having a siloxane skeleton.
However, when both ends of alternating copolymer 1 are —NCO, both ends of alternating copolymer 2 are —NH ₂ or —OH;
When both ends of alternating copolymer 1 are —NH ₂ , both ends of alternating copolymer 2 are —NCO. ) Both ends of alternating copolymer 1 are -NCO and both ends of alternating copolymer 2 are -NH ₂ or -OH,
The block copolymer according to claim 1. Both ends of alternating copolymer 1 are —NH ₂ , and both ends of alternating copolymer 2 are —NCO,
The block copolymer according to claim 1. The alternating copolymer 2 is a polyurea alternating copolymer 2-1,
The block copolymer according to any one of claims 1 to 3. The alternating copolymer 2 is a polyurethane-based alternating copolymer 2-2,
The block copolymer according to any one of claims 1 to 3. The diisocyanate compound <A> is a compound represented by the following formulas (I) to (X),
In the following formulas (I) to (X), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or alkyl having 1 to 7 carbon atoms,
X is each independently alkylene having 1 to 7 carbon atoms,
Y is each independently oxygen, sulfur, linear or branched alkylene having 1 to 7 carbon atoms, -C (CF ₃ ) ₂ -or -SO _2-
The block copolymer according to any one of claims 1 to 5.

A block copolymer according to any one of claims 1 to 6;
A solvent for dissolving the block copolymer;
Resin composition. The solvent is 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-dimethylpropionamide, tetramethylurea, at least one of dimethyl sulfoxide,
The resin composition according to claim 7. A solid content obtained by removing the solvent from the resin composition according to claim 7 or claim 8,
Paint film. It formed from the solid which removed the said solvent from the resin composition of Claim 7 or Claim 8,
Resin film. A resin film comprising at least two layers formed from a solid obtained by removing the solvent from the resin composition according to claim 7 or claim 8,
Resin film. It is a resin film (H) formed from the solid which removed the said solvent from the resin composition of Claim 7 or Claim 8, Comprising: The said block copolymer is a block copolymer of Claim 4, With the resin film (H);
It is resin film (S) formed from the solid which removed the said solvent from the resin composition of Claim 11, Comprising: The said block copolymer is a block copolymer of Claim 5, Resin, Film (S) and
Resin film. Comprising three layers laminated in the order of the resin film (H) / the resin film (S) / the resin film (H),
The resin film according to claim 12. Comprising three layers laminated in the order of the resin film (S) / the resin film (H) / the resin film (S),
The resin film according to claim 12. A resin film according to any one of claims 10 to 14;
OLED device. An OLED device according to claim 15;
Light emitting device.

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