JP7192166B2 - Block copolymer, resin composition, coating film, resin film, OLED element, light-emitting device, and method for producing block copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel urea- or urethane-based block copolymer, which is useful as a highly elastic recovery material for use in flexible devices in the field of electronic information materials, and a method for producing the same. Furthermore, it relates to materials that can be horizontally deployed for various applications such as automobiles, building materials, and life sciences.

In recent years, LCD (liquid crystal display) terminals, which are portable and can be used outdoors, have spread remarkably, and smartphones, mobile terminals such as PNDs (personal navigation devices), and wearable displays such as Google Glass have become popular. Examples include:
Furthermore, with the practical use of organic EL displays, there is a demand for further weight reduction, and a method of switching part of the members from glass or thin film glass to plastic has been taken. However, while thin glass has excellent heat resistance, it is extremely fragile. Plastics (especially PET, PC, PMMA, cycloolefin, etc.) are lightweight and highly transparent, but are resistant to impact and scratching. Therefore, the development of new functional plastics has been demanded.

Patent Literature 1 discloses a coating agent for glass substrates having excellent scratch resistance and excellent adhesion to glass and anti-scattering properties (paragraph 0019). However, although the obtained glass coating layer has excellent scratch resistance and anti-scattering properties, it is insufficient for use in recent smartphones and wearable displays.
On the other hand, in Patent Document 2, a new resin having high hardness and toughness and excellent heat resistance is useful as various rolls such as calendar rolls used in paper manufacturing, textiles, magnetic tapes, casters and other general molding resins. (Paragraph 0001). However, this technology relates to a general molding resin that is used by injecting it into a mold, and was not intended to be applied to film-like mobile terminals in terms of handling.
Furthermore, in Patent Document 3, it is possible to obtain by heat treatment at a low temperature, has good adhesion to the base material and sealing material, has improved tin plating resistance, and furthermore has warpage. It has excellent heat resistance, solder flux resistance, solvent resistance, chemical resistance, bending resistance, and electrical properties. A polyimidesiloxane-based insulating film composition for forming an insulating film of a component or the like is disclosed. However, the technique is intended to be applied to a flexible wiring board, and does not consider the transparency required for display applications.

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

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

Furthermore, the novel block copolymer of the present invention has an amine or isocyanate at the molecular end and a urea structure or a urethane structure in the molecule. Reaction with meth)acrylate is possible, and vinyl functional groups can be easily introduced.

As a result of extensive research in order to achieve the above object, the inventor of the present invention has
Aliphatic diisocyanate compound <A> having a cyclic structure in the molecule, alternating copolymer 1 obtained by polyaddition reaction of diamine compound <B>,
Aliphatic diisocyanate compound <A> having a cyclic structure in the molecule and alternating copolymer 2, which is a polyaddition product of specific diamine compound <C ¹ > or diol compound <C ² >, was further polyadded. 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 provided 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 polyaddition copolymer of Alternating Copolymer 1 below and Alternating Copolymer 2 below, containing repeating units represented by formula (3) and having a weight average molecular weight of 5,000 to 1,000,000. A block copolymer whose ends are either —NH ₂ —OH or —NCO, which may be end-capped.
- [(alternating copolymer 1) - (alternating copolymer 2)] - formula (3)
Alternating copolymer 1:
A polyaddition copolymer of a diisocyanate compound <A> and a diamine compound <B>, which has the formula (1)
-[(A)-(B)]- Formula (1)
A polyurea-based alternating copolymer having a repeating unit represented by and having a weight average molecular weight of 500 to 300,000 and both ends being —NH ₂ or —NCO;
Alternating copolymer 2:
A polyaddition copolymer of a diisocyanate compound <A> and a diamine compound <C ¹ >, represented by formula (2-1)
-[(A)-(C ¹ )]- Formula (2-1)
Polyurea-based alternating copolymer 2-1 containing repeating units represented by, having a weight average molecular weight of 500 to 300,000, and having -NCO or -NH ₂ at both ends,
and a polyaddition copolymer of a diisocyanate compound <A> and a diol compound <C ² >, which has the formula (2-2)
-[(A)-(C ² )]- Formula (2-2)
At least one alternating copolymer selected from polyurethane-based alternating copolymers 2-2 having a repeating unit represented by and having a weight average molecular weight of 500 to 300,000 and having —NCO or —OH at both ends ;
(wherein (A) is at least one aliphatic isocyanate structural unit independently having a cyclic structure in the molecule;
(B) are each independently at least one structural unit selected from aromatic diamines, aromatic diamines having an ether bond, and aliphatic diamines having a cyclic skeleton;
(C ¹ ) is 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.
provided that when both terminals of alternating copolymer 1 are —NCO, both terminals 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 terminals of alternating copolymer 1 are —NCO, and both terminals of alternating copolymer 2 are —NH ₂ or —OH.
[3] The block copolymer according to [1], wherein both terminals of alternating copolymer 1 are -NH ₂ and both terminals 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-based alternating copolymer 2-1.
[5] The block copolymer according to any one of [1] to [3], wherein the alternating copolymer 2 is a polyurethane alternating copolymer 2-2.
[6] The diisocyanate compound <A> is a compound represented by the following formulas (I) to (X),
In formulas (I) to (X) below, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or alkyl having 1 to 7 carbon atoms,
each X is independently an 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 —;
[1] The block copolymer according to any one of [5].

[7] the block copolymer according to any one of [1] to [6];
and a solvent that dissolves the block copolymer.
[8] The solvent includes 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], containing at least one of 4-methyl-2-pentanone, N,N-dimethylpropionamide, tetramethylurea, and dimethylsulfoxide.
[9] A coating film comprising a solid content obtained by removing the solvent from the resin composition according to [7] or [8].
[10] A resin film formed from a solid content obtained by removing the solvent from the resin composition according to [7] or [8].
[11] A resin film comprising at least two layers of a resin film formed from a solid content obtained by removing the solvent from the resin composition according to [7] or [8].
[12] A resin film (H) formed by removing the solvent from the resin composition of [7] or [8], wherein the block copolymer is the block of [4] a resin film (H), which is a copolymer;
A resin film (S) formed from a solid content obtained by removing the solvent from the resin composition according to [7] or [8], wherein the block copolymer is the block copolymer according to [5] A resin film comprising: a resin film (S);
[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 element of [15].

The block copolymer obtained by the present invention is soluble in general-purpose organic solvents, and exhibits excellent transparency, heat resistance, film-forming properties, and flexibility.

4 is a photograph showing the appearance of a coating film in Example 4. FIG. 4 is a photograph showing the appearance of a self-supporting film in Example 4. FIG. 4 is a photograph showing the appearance of a coating film in Comparative Example 2. FIG. 4 is a photograph showing the appearance of a self-supporting film in Comparative Example 2. FIG. It is a photograph after the glass protective property test of Example 11 (a). It is a photograph after the glass protective property test of Example 11 (b). It is a photograph after the glass protective property test of Example 12(a). It is a photograph after the glass protective property test of Example 12(b). It is a photograph after the glass protective property test of Example 13(a). It is a photograph after the glass protective property test of Example 13(b). It is a photograph after the glass protective property test of Example 14 (a). It is a photograph after the glass protective property test of Example 14(b). It is a photograph after the glass protective property test of Example 15 (a). It is a photograph after the glass protective property test of Example 15(b). It is a photograph after the glass protective property test of Example 16 (a). It is a photograph after the glass protective property test of Example 16(b). It is a photograph after the glass protective property test of Example 17 (a). It is a photograph after the glass protective property test of Example 17(b). It is a photograph after the glass protective property test of Example 18 (a). It is a photograph after the glass protective property test of Example 18(b). It is a photograph after the glass protective property test of Example 19 (a). It is a photograph after the glass protective property test of Example 19(b). It is a photograph after the glass protective property test of Example 20 (a). It is a photograph after the glass protective property test of Example 20(b). It is a photograph after the glass protective property test of Example 21. It is a photograph after the glass protective property test of Example 22. It is a photograph after the glass protective property test of Example 23. It is a photograph after the glass protective property test of Example 24. It is a photograph after the glass protective property test of Comparative Example 11 (a). It is a photograph after the glass protective property test of Comparative Example 11(b). It is a photograph after the test of the glass protective property test of Comparative Example 12 (a) (b). It is a photograph after the glass protective property 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. form part of the content of The invention will be more fully understood from the detailed description that follows. Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. However, the detailed description and specific examples are preferred embodiments of the invention and are given for purposes of illustration only. Various alterations and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description. Applicant does not intend to offer to the public any of the described embodiments, and any modifications, alternatives, which may not literally fall within the scope of the claims, may not be included under the doctrine of equivalents. part of the invention of

The block copolymer, the method for producing the block copolymer, and the uses thereof according to the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.

The block copolymer of the present invention is a polyaddition copolymer of Alternating Copolymer 1 below and Alternating Copolymer 2 below, containing repeating units represented by formula (3), and having a weight average molecular weight of It is a block copolymer having a molecular weight of 5,000 to 1,000,000 and which is either —NH ₂ —OH or —NCO, which may be terminal-blocked.
- [(alternating copolymer 1) - (alternating copolymer 2)] - formula (3)
provided that when both terminals of alternating copolymer 1 are —NCO, both terminals 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.
Elements constituting this block copolymer will be described in order below.

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

Alternating copolymer 1 is obtained by polyaddition of diisocyanate compound <A> and diamine compound <B>. Diisocyanate compound <A> and diamine compound <B> correspond to structural unit (A) and structural unit (B) in alternating copolymer 1, respectively. A 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. Specific examples thereof include the following formulas (I) to ( A diisocyanate compound represented by X) can be mentioned.
In formulas (I) to (X) below, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or alkyl having 1 to 7 carbon atoms,
each X is independently an alkylene having 1 to 7 carbon atoms,
Each Y is 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 compound having two isocyanate groups in the molecule, in which an isocyanate group is directly bonded to a linear or branched aliphatic hydrocarbon or an aliphatic ring carbon. .

Among the above specific examples, the diisocyanate compounds represented by the formulas (V), (VI) and (VIII) are preferred due to their 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, for example, disclosed in JP-A-2016-199694. compounds that are

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(isocyanatomethyl)furan, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, 4,4-isopropylidenebis(cyclohexylisocyanate), cyclohexane Diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2′-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanato-n-butylidene)pentaerythritol, dimer acid diisocyanate, 3,8-bis(isocyanatomethyl) tricyclodecane, 3,9-bis(isocyanatomethyl)tricyclodecane, 4,8-bis(isocyanatomethyl)tricyclodecane, 4,9-bis(isocyanatomethyl)tricyclodecane, 1,5-diisocyanatodecalin, 2,7-diisocyanate decalin, 1,4-diisocyanate decalin, 2,6-diisocyanate decalin, dicyclohexylsulfide-4,4'-diisocyanate, tricyclothiaoctane 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 particularly limited as long as it is a diamine compound independently selected from aromatic diamines, aromatic diamines having an ether bond, and aliphatic diamines having a cyclic skeleton. not something. For example, a diamine compound 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 An “aromatic diamine” is a compound having two amino groups in the molecule, in which the amino group is directly bonded to the 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-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 2,2'-diaminodiphenylpropane, benzidine, 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane, 1,1-bis[4-(4-aminophenoxy)phenyl]-4-methylcyclohexane, bis[4-(4-aminobenzyl) Phenyl]methane, 1,1-bis[4-(4-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-aminobenzyl)phenyl]-4-methylcyclohexane, 1,1-bis[4-(4-aminobenzyl)phenyl]methane , 4,4′-bis(4-aminophenoxy)biphenyl, 1,6-bis(4-((4-aminophenyl)methyl)phenyl)hexane, α,α′-bis(4-aminophenyl)-1 ,4-diisopropylbenzene, 1,4-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 preferred 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, diamine compounds <B> that can be used to impart high heat resistance include, for example, aliphatic diamines having a cyclic skeleton represented by formulas (XIII-1) and (XIII-2).

Examples thereof include aliphatic diamines having a cyclic skeleton represented by formulas (XIV-1) to (XIV-3).

Examples include aromatic diamines represented by formulas (XV-1) to (XV-5).

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

Examples thereof include aromatic diamines represented by formulas (XVII-1) to (XVII-4) and aromatic diamines having ether bonds represented by formulas (XVII-5) and (XVII-6).

Examples thereof include aromatic diamines represented by formulas (XVIII-1) to (XVIII-7) and aromatic diamines having ether bonds represented by formulas (XVIII-8) to (XVIII-11).

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

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)
Polyurea-based alternating copolymer 2-1 containing repeating units represented by, having a weight average molecular weight of 500 to 300,000, and having -NCO or -NH ₂ at both ends,
and a polyaddition copolymer of a diisocyanate compound <A> and a diol compound <C ² >, which has the formula (2-2)
-[(A)-(C ² )]- Formula (2-2)
Polyurethane-based alternating copolymer 2-2 containing repeating units represented by and having a weight average molecular weight of 500 to 300,000 and having —NCO or —OH at both ends
is at least one alternating copolymer selected from
(wherein (A) is at least one aliphatic isocyanate structural unit independently having a cyclic structure in the molecule;
(C ¹ ) is 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 one of the polyurea-based alternating copolymer 2-1 represented by the formula (2-1) and the polyurethane-based alternating copolymer 2-2 represented by the formula (2-2) is used. You may use it and 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) (C ¹ ) has a urea structure (-NH-CO-NH-), and the bonding site between the structural units (A) (C ² ) has a urethane structure (-NH-CO -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 physical properties of the block copolymer.

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

2.2 Diamine Compound <C ¹ > and Diol Compound <C ² >
The diamine compound <C ¹ > or the diol compound <C ² > used in the alternating copolymer 2 may be any one of them, and polyurea-based alternating copolymer 2 is obtained by polyaddition of each of them with the diisocyanate compound <A>. A copolymer 2-1 and a polyurethane alternating copolymer 2-2 can be obtained. Moreover, the diamine compound <C ¹ > and the diol compound <C ² > may be used in combination, and in this case, the alternating copolymer 2 becomes a copolymer containing both the urea structure and the urethane structure.

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

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

In particular, the diamine compound <C ¹ > that can be used to impart high transparency is a diamine compound 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 ,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 having 1 to 3 carbon atoms or phenyl, R ₇ is independently methylene, phenylene or phenylene in which at least one hydrogen is replaced with alkyl, and x is independently an integer of 1-6; y is an integer of 0-70;

Among the above specific examples, 1,12-diaminododecane, diethylene glycol bis(3-aminopropyl) ether, and a diamine compound having a siloxane skeleton represented by formula (XI) are preferable in terms of transparency and mechanical properties, and diethylene glycol bis(3 -Aminopropyl) ether, a diamine compound having a siloxane skeleton of formula (XI) can be particularly preferably used.

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, diamine compounds <C ¹ > that can be used to impart high transparency include, for example, linear aliphatic diamines represented by formulas (XII-1) to (XII-3), formula (XII -4) to (XII-8) include aliphatic diamines having an ether bond.

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

Examples of the aliphatic diamine having an ether bond represented by formula (XII-8) include Jeffamine D-230 (a=0, b=0, c=2, trade name, manufactured by Mitsui Fine Chemicals, Inc.). ~ 3), D-400 (a = 0, b = 0, c = 5 to 6), D-2000 (a = 0, b = 0, c = about 33), Jeffamine D series such as D-4000 Jeffamine ED-600 (b = 9.0, a + c = 3.6), ED-900 (b = 12.0, a + c = 3.6), ED-2003 (b = 38.7, a + c = 6 .0) Jeffamine ED series;

2.2.2 Diol compound <C ² >
The diol compound <C ² > is at least one selected from linear aliphatic diols, aliphatic diols having an ether bond, and diols having a siloxane skeleton. As the diol compound <C ² >, a compound having a structure obtained by replacing two —NH ₂ in the diamine compound <C ¹ > with —OH can be used.

Specific examples of the diol compound <C ² > are listed below, but are not limited to these examples.
Alkylene diol or polyoxyalkylene diol compounds include 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-cyclohexanedimethanol, methylpentanediol-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, Silaprene FM4401 (manufactured by JNC Co., Ltd., both terminal hydroxyl-modified silicon compound), Silaprene FM4411 (manufactured by JNC Corporation, both terminal hydroxyl-modified silicon compound, Mn = 1000), Silaprene FM4421 ( JNC Co., both terminal hydroxyl-modified silicon compound, Mn=5000) and Silaplane FM4425 (JNC Co., both terminal hydroxyl-modified silicon compound, Mn=10000). These are used alone or in combination of two or more.

3-Block Copolymer The block copolymer of the present invention contains a repeating unit represented by formula (3), which is a polyaddition copolymer of the above-described alternating copolymer 1 and alternating copolymer 2. , a block copolymer having a weight-average molecular weight of 5,000 to 1,000,000 and an optionally capped end of either —NH ₂ —OH or —NCO.
- [(alternating copolymer 1) - (alternating copolymer 2)] - formula (3)
Alternating copolymer 1 and alternating copolymer 2 are bonded via urea bonds or urethane bonds.

In the block copolymer of the present invention, when both terminals of alternating copolymer 1 are -NCO, both terminals of alternating copolymer 2 are _-NH2 or -OH; When the ends are —NH ₂ , both ends of Alternating Copolymer 2 are —NCO. Both of these terminal groups undergo a polyaddition reaction to form a urea bond or a urethane bond, resulting in the block copolymer of the present invention.

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

In the polyaddition reaction or polycondensation reaction, by changing the charge ratio (molar ratio) of the two types of monomers, it is possible to obtain an alternating copolymer having terminal groups corresponding to the monomer structure, or to obtain an alternating copolymer having an arbitrary molecular weight. can also be controlled. This is described in Billmeyer. F. W. ; Step-Reaction (Condensation) Polymerization. In Textbook of Polymer Science; John Wiley &Sons; Singapore, 1994; pp35-39. It is described in.

Based on the above theory, when both terminals of the alternating copolymer 1 constituting the block copolymer are —NCO, both terminals of the alternating copolymer 2 must be —NH ₂ or —OH, and vice versa. When both terminals of alternating copolymer 1 are _-NH2 , both terminals of alternating copolymer 2 must be -NCO.

For example, when producing an alternating copolymer 1 having —NCO at both ends, in the step (step 1) of polyaddition of the diisocyanate compound <A> and the diamine compound <B>, the diisocyanate compound <A> should be used in excess of the number of moles of the 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 are in a relationship of 1.06≦n1/n2≦1.9. Adjusting is preferred. In this manner, the weight average molecular weight of the alternating copolymer 1 having —NCO at both ends can be adjusted in the range of 500 to 300,000.

In that case, both ends of the alternating copolymer 2 are —NH ₂ or —OH, so that 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 the diamine compound <C ¹ > or the diol compound <C ² > may be used more than the number of moles of the diisocyanate compound <A>. For example, when the number of moles of diisocyanate compound <A> is n1, and the number of moles of diamine compound <C ¹ > or diol compound <C ² > is n2, the number of moles of each is 1.06≦n2/n1≦1. It is preferable to adjust so that the relationship of 0.9 is obtained. In this manner, the weight average molecular weight of the alternating copolymer 2 having —NH ₂ at both ends can be adjusted in the range of 500 to 300,000.

Further, for example, when producing an alternating copolymer 1 having —NH ₂ at both ends, in the step of polyaddition of the diisocyanate compound <A> and the diamine compound <B> (step 1), the diamine compound The number of moles of <B> may be used more than the number of moles of the diisocyanate compound <A>. 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 number of moles is in the relationship of 1.06≦n2/n1≦1.9. Adjusting is preferred. In this manner, the weight average molecular weight of the alternating copolymer 1 having —NH ₂ at both ends can be adjusted in the range of 500 to 300,000.

In that case, both terminals of the alternating copolymer 2 are —NCO, so 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 used more than the number of moles of the diamine compound <C ¹ > or the diol compound <C ² >. For example, when 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, the number of moles of each is 1.06≦n1/n2≦1. It is preferable to adjust so that the relationship of 0.9 is obtained. In this manner, the weight average molecular weight of the alternating copolymer 2 having —NCO at both ends can be adjusted in the range of 500 to 300,000.

Next, a method for producing a block copolymer will be described. The block copolymer is
(i) A method for 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 conducting a polyaddition reaction ( ii) A method for producing a block copolymer by introducing the alternating copolymer 1 obtained in step 1 into a reaction vessel and then performing step 2, (iii) the alternating copolymer obtained in step 2 Method (iv) for producing a block copolymer by introducing coalescing 2 into a reaction vessel and then performing step 1; Method for producing a copolymer (v) After carrying out step 2 in the same container, a stepwise production method exemplified by a method for producing a block copolymer by subsequently carrying out step 1 (hereinafter referred to as the step polymerization method) is adopted. A block copolymer can be obtained by any of the stepwise polymerization methods. You may adopt the method of carrying out repeatedly.

Next, the structural change of the block copolymer will be explained. Since the molecular weights of the alternating copolymers 1 and 2 can be arbitrarily controlled in the steps 1 and 2, block copolymers having different block chain lengths can be obtained. By changing the molar ratio of the alternating copolymer 1 and the alternating copolymer 2 obtained in steps 1 and 2, the molecular weight of the block copolymer can be controlled. The weight average molecular weight of the block copolymer is preferably in the range of 5,000 to 1,000,000, more preferably 5,000 to 300,000.

5 Other diisocyanate compounds <D>
In the block copolymer of the present invention, both the alternating copolymer 1 and the alternating copolymer 2 have structural units of the diisocyanate compound <A>, that is, aliphatic isocyanate structural units (A) having a cyclic structure. A part of the compound <A> may be replaced with another diisocyanate compound <D> (structural unit (D)). The other diisocyanate compound may be contained in part of the alternating copolymer 1, may be contained in part of the alternating copolymer 2, and may be contained in a portion to which each alternating copolymer is bonded. may be sandwiched between the structures, or may be bonded to the terminal of the block copolymer.

Other diisocyanate compounds are not particularly limited as long as they are compounds having two diisocyanate groups in the molecule other than the diisocyanate compound <A>. As specific examples of other diisocyanate compounds, the following compounds 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 and trioxyethylene diisocyanate. , 2,4′-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 disclosed in JP-A-2016-199694, aromatic diisocyanates, sulfur-containing aliphatic diisocyanates, aliphatic sulfide-based diisocyanates, aromatic sulfide-based diisocyanates, aliphatic Examples include sulfone-based diisocyanates, aromatic sulfone-based diisocyanates, sulfonic acid ester-based diisocyanates, aromatic sulfonic acid amide-based diisocyanates, and sulfur-containing heterocyclic diisocyanates. Specific examples of these diisocyanate compounds include the following compounds.

The aromatic diisocyanate referred to in the present invention is a compound having two isocyanate groups in the molecule, in which the isocyanate group is directly bonded to the carbon of the 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 the carbon of a heterocyclic ring containing a heteroatom.

Furthermore, the sulfide diisocyanate, sulfone diisocyanate, sulfonate ester diisocyanate, and sulfonamide diisocyanate of the present invention each have a sulfide, sulfone, sulfonate ester, or sulfonamide structure in the molecule, and It is a compound having two isocyanate groups 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-diisocyanato-4-isocyanatomethyloctane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, 1, 4-butylene glycol dipropyl ether ω,ω'-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 , 3,5,6-tetrabromo-p-xylylenediisocyanate, 4-methyl-m-xylylenediisocyanate, 4-ethyl-m-xylylenediisocyanate, bis(isocyanatoethyl)benzene, bis(isocyanatopropyl)benzene, 1 , 3-bis(α,α-dimethylisocyanatomethyl)benzene, 1,4-bis(α,α-dimethylisocyanatomethyl)benzene, α,α,α',α'-tetramethylxylylene diisocyanate, bis(isocyanate Butyl)benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl)phthalate, 2,6-di(isocyanatomethyl)furan, phenylene diisocyanate, tolylene diisocyanate, ethylphenylene diisocyanate, isopropyl phenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, naphthalene diisocyanate, methylnaphthalene 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, phenylisocyanatomethyl isocyanate, phenylisocyanatoethyl isocyanate, 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, dibenzofurandi isocyanate, carbazole diisocyanate, ethyl Carbazole diisocyanate , dichlorocarbazole diisocyanate

Sulfur-containing aliphatic diisocyanates; thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethylsulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, 1,2-bis(2-isocyanatoethylthio)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-isocyanato-2-isocyanatomethyl-3-thiapentane

Aliphatic sulfide-based diisocyanates; bis[2-(isocyanatomethylthio)ethyl]sulfide, bis(isocyanatomethyl)sulfide, bis(isocyanatoethyl)sulfide, bis(isocyanatopropyl)sulfide, bis(isocyanatohexyl)sulfide, bis(isocyanatomethyl) ) disulfide, bis(isocyanatoethyl) disulfide, bis(isocyanatopropyl) disulfide

Aromatic sulfide-based diisocyanates; diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzylthioether, bis(4-isocyanatomethylbenzene ) sulfide, 4,4′-methoxybenzenethioethylene glycol-3,3′-diisocyanate, diphenyl disulfide-4,4′-diisocyanate, 2,2′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3 , 3′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3,3′-dimethyldiphenyl disulfide-6,6′-diisocyanate, 4,4′-dimethyldiphenyl disulfide-5,5′-diisocyanate, 3,3 '-dimethoxydiphenyl disulfide-4,4'-diisocyanate, 4,4'-dimethoxydiphenyl disulfide-3,3'-diisocyanate

Aliphatic sulfone-based diisocyanates; bis(isocyanatomethyl) sulfone

Aromatic sulfone-based diisocyanates; 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'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodibenzylsulfone, 4,4'-dimethyldiphenylsulfone -3,3′-diisocyanate, 4,4′-di-tert-butyldiphenylsulfone-3,3′-diisocyanate, 4,4′-dimethoxybenzeneethylenedisulfone-3,3′-diisocyanate, 4,4′- Dichlorodiphenylsulfone-3,3'-diisocyanate

Sulfonic acid ester diisocyanates; 4-methyl-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol ester, 4-methoxy-3-isocyanatobenzenesulfonyl-4'-isocyanatophenol 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-diisocyanatomethyl, 1,4-dithiane-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanatomethyl, 1, 3-dithiolane-4,5-diisocyanate, 1,3-dithiolane-4,5-diisocyanatomethyl, 1,3-dithiolane-2-methyl-4,5-diisocyanatomethyl, 1,3-dithiolane-2,2- Diisocyanatoethyl, Tetrahydrothiophene-2,5-diisocyanate, Tetrahydrothiophene-2,5-diisocyanatomethyl, Tetrahydrothiophene-2,5-diisocyanatoethyl, Tetrahydrothiophene-3,4-diisocyanatomethyl, 2-(1,1-diisocyanate methyl)thiophene, 3-(1,1-diisocyanatomethyl)thiophene, 2-(2-thienylthio)-1,2-diisocyanatopropane, 2-(3-thienylthio)-1,2-diisocyanatopropane, 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-diisocyanato-2,4-dithiapentane, 2,5-(diisocyanatomethyl)thiophene, 2,3-(diisocyanatomethyl)thiophene, 2,4-(diisocyanatomethyl)thiophene, 3,4-(diisocyanatomethyl)thiophene, 2,5-(diisocyanatomethylthio)thiophene, 2,3-(diisocyanatomethylthio)thiophene, 2,4-(diisocyanatomethylthio)thiophene, 3,4-(diisocyanatomethylthio)thiophene, 2,4-bisisocyanatomethyl-1,3,5-trithiane

Diisocyanate compounds are generally used to produce polyurea and polyurethane, and are industrially produced by reacting the corresponding diamine as a starting material with phosgene. That is, the desired diisocyanate compound <A> and other diisocyanate compounds can be produced using the diamine compound <B> as a starting material.

6-Block Copolymer Terminations The end groups of the block copolymers of the basic invention are either —NH ₂ —OH or —NCO, but these end groups may be capped. By blocking the ends, the storage stability of the block copolymer can be improved. Terminal blocking agents exemplified below can be used to block terminal groups.

When the terminal group is -NCO, a compound having _-NH2 group, -OH group, -COOH group, -SO2H group can be used as a terminal blocking agent.

Specific examples of compounds having —NH ₂ groups that can be used as endcapping agents include 1-aminobutane, 4-ethynylaniline, 3-ethynylaniline, propargylamine, 3-aminobutyne, 4-aminobutyne, 5-aminopentyne. , 4-aminopentyne, allylamine, 7-aminoheptyne, m-aminostyrene, p-aminostyrene, m-amino-α-methylstyrene, 3-aminophenylacetylene, 4-aminophenylacetylene. Among these, 1-aminobutane is preferred because of its excellent reactivity. These monoamine compounds may be used alone or in combination of two or more.

Specific examples of compounds having —OH groups that can be used as terminal blockers include monoalcohol compounds having 1 to 18 carbon atoms. Examples of monoalcohol compounds 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, tri decyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, etc.); branched monools (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 (such as cyclohexanol) and aromatic ring-containing monools (such as benzyl alcohol)]. Furthermore, specific examples of compounds having an —OH group include polymer monools (polyester monools, polyether monools, polyether ester monools, etc.), cellosolves and carbitols.
Among these, linear monools are preferred. Specifically, they are 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 the terminal blocking agent, a general urethanization catalyst such as dibutyltin dilaurate can be used as the reaction catalyst. Examples of urethanization catalysts include various nitrogen-containing compounds such as N,N-dimethylaminoethyl ether, triethylamine, triethylenediamine, and N-methylmorpholine, and various nitrogen-containing compounds such as potassium acetate, zinc stearate, and tin octylate. Examples 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 or} —OH, a compound having —NCO group can be used as a terminal capping agent.

Specific examples of the —NCO group-containing compound that can be used as a terminal blocking agent include phenyl isocyanate, toluylene isocyanate, dimethylphenyl 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 terminal blocking agent, a general urethanization catalyst such as dibutyltin dilaurate can be used as the reaction catalyst. Examples of urethanization catalysts include various nitrogen-containing compounds such as N,N-dimethylaminoethyl ether, triethylamine, triethylenediamine, and N-methylmorpholine, and various nitrogen-containing compounds such as potassium acetate, zinc stearate, and tin octylate. Examples include metal salts, various organic metal compounds such as dibutyltin dilaurate, and chelate compounds such as zirconium tetraacetylacetonate.

7. Reaction Solvent The solvent used in producing the alternating polymer 1, the alternating polymer 2, and the block copolymer of the present invention is not particularly limited as long as these copolymers can be synthesized. Examples of reaction solvents include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, Diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl Ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether (1-methoxy- 2-propanol), triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, 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-diethyl formamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethyl Ru-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 Mention may be made of propyl alcohol, N,N-dimethylpropionamide, tetramethylurea, and dimethylsulfoxide.

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 -2-Pentanone, N,N-dimethylpropionamide, tetramethylurea, and dimethylsulfoxide are preferred because the polyurea-based alternating copolymer has good solubility and uniform polymerization proceeds.
These reaction solvents may be used alone or in combination of two or more. Furthermore, other solvents can be mixed and used in addition to the above reaction solvents.

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

8 Uses of Block Copolymer The block copolymer of the present invention can be utilized as a material for protecting image display elements from impact in the field of image display elements such as liquid crystal displays and organic EL displays. . For example, in a liquid crystal display, it may be a film or a coating material placed on the front or back surface of a cover glass or cover film, or on the front or back surface of a polarizing plate. Organic EL displays are becoming thinner and lighter due to flexibility, and the need to protect the elements from external forces such as impacts has become extremely high. Along with this, the block copolymer of the present invention is useful as the front and back surfaces of cover glasses and cover films, the front and back surfaces of polarizing plates, back films to be installed on element bodies, and coating materials. It can also be used as a material inside the device such as a fill material, a sealing material, a dam material, a buffer material, and a planarizing film.

In the automobile field, it is also useful as a material for protecting the exterior and interior of automobiles from impact. For example, a paint protection film or coating material may be used to protect the exterior paint from being damaged by flying stones or the like. Taking advantage of the excellent impact absorption properties of block copolymers, it may be used as a film or coating material installed in the interlayer film of laminated glass for automobiles, glazing, rear windows, rearview mirrors, sensors, and the like.

Polyurea and polyurethane-based materials also have potential uses as biocompatible materials. It is also expected to be applied to medical devices that require blood compatibility, such as filtering by spinning such as electrospinning to make dialysis membranes, hollow fibers such as heart-lung machines, and coating needles for intravenous drips that are buried in the body for a long time. can.

In the field of building materials, it can be used as a film or coating material for the purpose of preventing scattering of window glass, for example, as a film or coating material to prevent the window glass of high-rise buildings from breaking, scattering and falling during an earthquake or earthquake, or for security purposes. It is good also as breakage prevention of glass. Polyurea is known to enhance the impact resistance of structural buildings, such as concrete and block walls, by coating them. good.
The polyurea-based alternating copolymer can also be used for the same purposes as the block copolymer.

9 Resin Composition The resin composition of the present invention is a composition containing the block copolymer; and a solvent for dissolving the block copolymer.
The solvent used in the resin composition of the present invention is not particularly limited as long as it can dissolve the block copolymer. For example, the reaction solvent used in the production of the block copolymer can be used as it is, or another solvent can be added and used as a mixed solvent.
Moreover, after isolating the block copolymer as a solid content, it can be used by redissolving it in a desired solvent. As a method for 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, or isopropyl ether to precipitate the block copolymer. and separating by filtration, washing, drying, or the like. By carrying out such an operation, it is also possible to remove the catalyst used in the production of the block copolymer.
Particularly preferred solvents include propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, 4 -methyl-2-pentanone, N,N-dimethylpropionamide, tetramethylurea, dimethylsulfoxide. These solvents may be used alone or in combination of two or more. The use of these solvents is preferable because precipitation of the polymer can be prevented during 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 terms of solubility and reactivity, it 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 coating film forming method, 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 in the range of 10 to 50,000 mPa·s.

Additives such as ultraviolet absorbers and light stabilizers (HALS) may be further added to the resin composition of the present invention.

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

UV absorbers include Adekastab LA-46, Adekastab LA-77Y, Adekastab LA-63P, Adekastab LA-72, Adekastab LA-32, and Tinuvin 479, Tinuvin 292, Tinuvin 123 and Tinuvin manufactured by BASF. 384-2, Tinuvin 400 and the like.

The amount of ultraviolet 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.

Light stabilizers (HALS) include TINUVIN (registered trademark) 5100 (neutral general-purpose HALS) manufactured by BASF, and TINUVIN292 (compound name: bis(1,2,2,6,6-pentamethyl-4-piperidinyl). sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), TINUVIN152 (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), TINUVIN144 (compound name: bis(1,2,2,6,6- pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate), TINUVIN123 (compound name: decanedioic acid, bis(2,2, Reaction product of 6,6-tetramethyl-1-(octyloxy)-4 piperidinyl) ester (in the presence of 1,1-dimethylethyl hydroperoxide and octane), TINUVIN111FDL (about 50%, TINUVIN622, compound name: (butanedioic acid polymer (4-hydroxy-2,2,6,6-tetramethyl piperidinyl-yl) in the presence of ethanol), about 50%, CHIMASSORB119, compound name: N-N'-N''-N'' '-tetrakis(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4,7-diazadecane-1, 10-diamine), or Adekastab LA series manufactured by Adeka Co., Ltd., specifically LA-52 ((5)-6116), LA-57 ((5)-5555), LA-62 ((5) -5711), LA-67 ((5)-5755). The numbers in parentheses are the numbers of existing chemical substances stipulated by the Law Concerning the Examination of Chemical Substances and Regulation of Their Manufacture, etc. in Japan (Chemical Substances Control Law).

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, if necessary, active energy ray sensitizers, polymerization inhibitors, waxes, plasticizers, leveling agents, surfactants, dispersants, antifoaming agents, wettability improvers, antistatic agents, curing aids, Various additives such as additives that impart antifouling properties and low-friction properties, additives that impart scratch resistance, heat stabilizers, flame retardants, and 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. Block copolymers are soluble in general-purpose organic solvents and have good heat resistance and mechanical properties.
The resin composition of the present invention may be a composition containing the polyurea-based alternating copolymer; and a solvent for dissolving the polyurea-based alternating copolymer.

10. Coating Film The coating film of the present invention can be obtained by forming the resin composition of the present invention on a supporting substrate or structure by a method such as coating, printing or casting, and then removing the solvent. The removal method may be, for example, drying, and the drying method is not particularly limited. Heat (hot air) drying, vacuum drying, vapor drying, barrel drying, spin drying, suction drying and the like can be mentioned.
The drying method or drying conditions may be appropriately selected according to 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, heat treatment using an air circulation type constant temperature oven, a heater using microwaves 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. For example, the drying temperature may be 40 to 250° C. and the drying time may be 1 minute to 24 hours. Heating may be performed in two steps, and if necessary, heat drying may be performed in a nitrogen atmosphere or under reduced pressure.
The shape of the coating film from which the solvent has been removed may be determined according to the use described in the above "Use of block copolymer". Alternatively, the solvent may be distilled off after applying the resin composition to the target portion.
Such a configuration is preferable because it forms a flat coating film.

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

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

Formation of the resin film is not particularly limited as long as it is a method capable of producing a thin film. A wet coating method (coating method) other than the method using an applicator used in the examples may be used. Excellent surface smoothness can be obtained by using a coating method. Among the coating methods, the spin coating method and the bar coating method, which are simple and capable of forming a uniform film, can be used when producing a small amount. In the case of roll-to-roll, which emphasizes productivity, gravure coating, die coating, reverse coating, roll coating, slit coating, dipping, spray coating, kiss coating, reverse kiss coating, air A knife coating method, a curtain coating method, a rod coating method, an inkjet method, and the like can be mentioned. In addition, methods using various printing apparatuses such as letterpress printing, intaglio printing, lithographic printing, and stencil printing can be used. These methods may be appropriately selected according to the required thickness, viscosity, curing conditions, and the like.

12 OLED device The OLED device of the present invention comprises the resin film of the present invention. OLED elements may be of either rigid or flexible type. Due to 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 conventional glass substrates and polyethylene naphthalate (PEN) film substrates in bottom emission type flexible OLED devices. be able to. Alternatively, it can be laminated onto or under a conventional substrate and used as a shock absorbing film.
In a top emission type flexible OLED element, it can be used as a sealing film in place of the sealing glass. Alternatively, it can be laminated on or under conventional sealing glass and used as a shock absorbing film. Alternatively, it can be used as a transparent substrate instead of a conventional glass substrate, polyimide (PI) film substrate, or polyethylene naphthalate (PEN) substrate.
Ordinary polyurea resins have excellent properties such as heat resistance and mechanical strength. Therefore, it was difficult to apply it to the field of electronic information materials, which requires precision coating.
However, since the present invention has made it possible to synthesize polyurea resins that are soluble in general-purpose organic solvents, it is possible to apply the resin composition to a desired location by coating and drying it, making it possible to apply it to the field of electronic information. It has become possible.
Since the OLED element of the present invention is provided with a layer that absorbs impact, it is possible to prevent breakage of the OLED element.

13 Light Emitting Device The light emitting device of the present invention comprises the OLED element of the present invention. Examples of light-emitting devices include organic EL displays, particularly flexible organic EL displays, and organic EL lighting, particularly flexible organic EL lighting.
The organic EL display is not particularly limited as long as it includes the OLED element of the present invention. Examples include televisions, personal digital assistants, wearable systems, in-vehicle displays, and digital signage.
Since the present invention provides an impact-absorbing layer, it is possible to prevent failure of the light-emitting device due to breakage of the OLED element.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples.

The symbols used in the examples have the following meanings.
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 (manufactured by Kanto Chemical Co., Ltd., dehydrated)
THF: Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., for high-performance liquid chromatography)
DMF: N,N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography)
DEF: N,N-diethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
HXDI: 1,3-bis(isocyanatomethyl)cyclohexane (manufactured by Mitsui Chemicals, Inc., product name; Takenate 600)
Solmix AP-1: ethanol, 2-propanol, methanol, water mixture (manufactured by Nippon Alcohol Sales)
Silaplane FM4411: silicon compound modified with hydroxyl at both ends, hydroxyl equivalent: 564 g/mol (manufactured by JNC Co., Ltd.)
Silaplane FM3311: α, ω-(3-aminopropyl) polydimethylsiloxane (manufactured by JNC Corporation)
ORGATICS ZC-150: Zirconium tetraacetylacetonate (manufactured by Matsumoto Fine Chemicals 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>
Apparatus: LC-2000Plus series manufactured by JASCO Corporation (detector: differential refractometer)
Solvent: THF/DMF = 1/1 (v/v)
Flow rate: 0.5ml/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
Standard sample for calibration curve: PSt

1 Block copolymer [Production example 1] Synthesis of alternating copolymer (1) Under a nitrogen atmosphere, BAPP (14.3 g), DMAc ( 57.4 g) were introduced. It was heated to 120° C. using an oil bath. Then, a solution of HXDI (5.66 g) dissolved in DMAc (22.6 g) was introduced all at once with a syringe to initiate the reaction (HXDI:BAPP=1.0:1.2, molar ratio). After that, while maintaining the temperature at 120° C., the mixture was stirred for 6 hours to obtain a transparent reaction liquid. Mw determined by GPC analysis of the reaction solution was 8,200, and PDI was 2.7.
Further, Solmix AP-1 (600 mL) was prepared in a 1-L beaker, and the resulting polymerization liquid (20 mL) was slowly added dropwise using a Pasteur while stirring with a stirrer. A white solid precipitated in the solution. After the precipitate was collected by suction filtration, it was dried in a vacuum dryer set at 120° C. for 6 hours to obtain the target alternating copolymer (1).

[Production Example 2] Synthesis of Alternating Copolymer (2) Under a nitrogen atmosphere, HXDI (51.1 g) and DMAc (249.0 g) were added to a 1,000 mL three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel. was introduced. While the flask was immersed in a water bath and maintained in a cooled state, a solution in which Silaplane FM4411 (198.8 g) was dissolved was dropped using a dropping funnel to initiate the reaction (HXDI: FM4411 = 1.5: 1, mol ratio). After that, the reaction was continued for 6 hours to obtain a transparent reaction liquid. GPC analysis of the reaction mixture gave an Mw of 6,100 and a PDI of 1.9, yielding the desired alternating copolymer (2).

[Production Example 3] Synthesis of alternating copolymer (3) In a nitrogen atmosphere, HXDI (4.26 g) and DMAc (57.6 g) were introduced into a 200 mL three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel. did. After that, it was heated at 40° C. using an oil bath. A solution of DMAc (14.4 g) dissolved in FM3311 (13.74 g) was added dropwise to initiate the reaction (HXDI:FM3311=1.5:1, molar ratio). After that, the mixture was stirred at the same temperature for 5 hours to obtain a transparent reaction solution. GPC analysis of the reaction solution gave an Mw of 9,900 and a PDI of 3.2, yielding the desired alternating copolymer (3).

[Production Example 4] Synthesis of alternating copolymer (4)
DMAc (750.6 g) was introduced into the alternating copolymer (2) synthesized in [Production Example 2] to adjust the concentration to 20%. Further, methanol (8.4 g) was introduced and stirred for 30 minutes to react the terminal isocyanate groups of the alternating copolymer (2) with methanol, and the alternating copolymer (4) was obtained by inactivation. rice field.

[Production Example 5] Synthesis of alternating copolymer (5)
Methanol (0.7 g) was introduced into the reaction solution in which the alternating copolymer (3) synthesized in [Manufacturing Example 3] was heated to 40°C, and the mixture was stirred for 30 minutes to form the terminal of the alternating copolymer (3). An alternating copolymer (5) was obtained by reacting isocyanate groups with methanol and inactivating them.

[Example 1] Synthesis of block copolymer (1) Under a nitrogen atmosphere, the alternating copolymer obtained in [Production Example 1] was placed in a three-necked flask (200 mL) equipped with a reflux condenser, a thermometer and a dropping funnel ( 1) (5.02 g) was introduced followed by DMAc (20.0 g). 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, the dropping was started immediately, and the alternating copolymer (1) and the alternating copolymer (2) were uniformly mixed in the flask while stirring (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 transparent and had an Mw of 61,000 and a PDI of 6.0 as determined by GPC analysis.

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

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

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

[Comparative Example 1] Fabrication of film (3) by mixing alternating copolymer (1) and alternating copolymer (4) 1.00 g of alternating copolymer (1) synthesized in [Production Example 1] was added with 4.5 g of DMAc. 02 g was added to prepare a solution with a solid concentration of 20 wt %. Further, a 20 wt % solution of the alternating copolymer (1) and the alternating copolymer (4) synthesized in [Production Example 4] were mixed to obtain an alternating copolymer (1):alternating copolymer (4)=1:3. (weight ratio). The mixed solution was a cloudy, heterogeneous solution.
This 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 to obtain a cloudy film (3). As a result of peeling the film (3) from the aluminum substrate, a free-standing film could not be obtained.

[Comparative Example 2] Production of film (4) by mixing alternating copolymer (1) and alternating copolymer (5) To 1.00 g of alternating copolymer (1) synthesized in [Production Example 1] was added DMAc 4. 02 g was added to prepare a solution with a solid concentration of 20 wt %. Further, a 20 wt % solution of the alternating copolymer (1) and the alternating copolymer (5) synthesized in [Production Example 5] were mixed to obtain an alternating copolymer (1):alternating copolymer (5)=1:3. (weight ratio). The mixed solution was a cloudy, heterogeneous solution.
This mixed solution (1.00 g) was applied to an aluminum base material and heated on a hot plate heated to 120° C. for 1 hour to remove the solvent, whereby a cloudy film (4) was obtained. As a result of peeling the film (4) from the aluminum substrate, a free-standing film could not be obtained.

From Table 1, it can be seen that Examples 3 and 4 are clearly different from Comparative Examples 1 and 2, and that the desired block copolymers were obtained.

2 Resin film [Production Example 11] Synthesis of polymer (11) as alternating copolymer
In a nitrogen atmosphere, BAPP (4.06 g) was placed in a 100 ml three-necked flask equipped 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 prepared by dissolving HXDI (1.94 g) in DEF (5.3 ml) prepared in advance in a 30 ml sample bottle was added using a funnel (BAPP:HXDI=1:1.01, mol ratio). The DEF solution of HXDI remaining in the 30 ml sample bottle was washed with DEF (2.9 ml) and added to the reaction solution. Then, after reacting for 4 hours while maintaining the temperature at 120° C., the mixture was cooled in a water bath, and 1 ml of methanol was added to quench excessive isocyanate groups. Polymer (11), which is a polyurea polymer containing structural units of the intended alternating copolymer, was obtained with Mw of 126,000 and PDI of 20.0 as determined by GPC analysis of the reaction solution.

[Production Example 12] Synthesis of polymer (12) as an alternating copolymer
Under a nitrogen atmosphere, HXDI (2.7 g) and DMAc (50.1 g) were introduced into a 200 mL three-necked flask equipped with a reflux condenser, thermometer and dropping funnel. While the flask was immersed in a water bath and maintained in a cooled state, Silaplane FM3311 (12.3 g) was added dropwise over 5 minutes using a dropping funnel (HXDI:FM3311=1.06:1, molar ratio). Further, FM3311 adhering to the dropping funnel was washed away using DMAc (10.0 g) and introduced into the flask. After that, the reaction was continued for 2 hours to obtain a transparent reaction solution. The reaction solution was found to have an Mw of 34,000 and a PDI of 7.0 as determined by GPC analysis. Polymer (12), which is a polyurea-based polymer containing structural units of the desired alternating copolymer, was obtained.

[Production Example 13] Synthesis of polymer (13) as a block copolymer
Synthesis of Alternating Copolymer 1 Represented by Formula (1):
Under a nitrogen atmosphere, BAPP (71.7 g) and DMAc (287.0 g) were introduced into a 1000 mL three-necked flask equipped with a reflux condenser, thermometer and dropping funnel. It was heated to 120° C. using an oil bath. Then, 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 initiate the reaction (HXDI: BAPP = 1.0: 1.2 , molar ratio). After that, while maintaining the temperature at 120° C., the mixture was stirred for 5 hours to obtain a transparent reaction liquid. Mw determined by GPC analysis of the reaction solution was 17,000, and PDI was 3.5.
Further, a mixed solution of Solmix AP-1 (2160 mL) and acetone (240 ml) was prepared in a 3 L beaker, and the resulting polymerization solution (82 g) was slowly added dropwise using a Pasteur while stirring with a stirrer. A white solid precipitated in the solution. The precipitate was collected by suction filtration. The same operation was repeated four times to obtain a white solid containing a solvent. The resulting white solid was dried in a vacuum dryer set at 120° C. for 6 hours to obtain 59 g of the target alternating copolymer 1 represented by formula (1).

Synthesis of Alternating Copolymer 2 Represented by Formula (2-1):
Under 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, thermometer and dropping funnel. After that, it was heated at 40° C. using an oil bath. A solution of DMAc (80.2 g) dissolved in FM3311 (73.3 g) was added dropwise to initiate the reaction (HXDI:FM3311=1.5:1, molar ratio). After that, the mixture was stirred at the same temperature for 6 hours to obtain a transparent reaction solution. The Mw and PDI of the reaction liquid determined by GPC analysis were 11,000 and 4.0, respectively.

Synthesis of block copolymers:
Under a nitrogen atmosphere, a reaction solution (375.0 g) of alternating copolymer 2 represented by formula (2-1) was introduced into a three-necked flask (1000 mL) equipped with a reflux condenser, a thermometer and a dropping funnel. Then, it was heated to 120°C using an oil bath. A solution obtained by mixing 24.9 g of alternating copolymer 1 represented by formula (1) and DMAc (119.5 g) was introduced into the dropping funnel (copolymer concentration: 19%). After that, the dropping was started immediately, and the alternating copolymer 1 and the alternating copolymer 2 were uniformly mixed and reacted in the flask while stirring (alternating copolymer 1:alternating copolymer 2=1:3, weight ratio). By stirring at the same temperature for 5 hours, a desired block copolymer, polymer (13), was obtained. The resulting reaction solution was transparent and had an Mw of 98,000 and a PDI of 9.3 as determined by GPC analysis.

[Production Example 14] to [Production Example 17] Synthesis of polymer (14) to polymer (17)
Polymer (14 ) to polymer (17) were synthesized.

[Production Example 18] to [Production Example 20] Synthesis of polymer (18) to polymer (20)
Composition such as molar ratio, weight ratio, etc., FM3311 was changed to FM4411, and 0.5 wt% of ORGATIX ZC-150 was added as a catalyst to the total weight of HXDI and FM4411. Polymer (18) to Polymer ( 20) was synthesized.

[Production Example 21] Synthesis of polymer (21)
Polymer (21), which is a desired block copolymer, was synthesized in the same manner as in [Production Example 15] except that the molar ratio and reaction scale were different.

[Production Example 22] Synthesis of polymer (22)
The desired block copolymerization was carried out 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) were set to 25 ° C. A coalescing polymer (22) was synthesized.

Table 2 shows the composition, Mw, and PDI of Polymers (11) to (22) obtained.

[Example 11] Preparation of resin film (11) A release film (product name: NSD-100, 100 µm, manufactured by Fujimori Industry Co., Ltd.) was used as a substrate. Cast the polymer (11) synthesized in Production Example 11 (concentration: 19%, solvent: DEF) to the substrate, baker type film applicator (product name: No. 510 baker type film applicator, manufactured by Yasuda Seiki Co., Ltd. ) to adjust the distance between the applicator and the substrate by adjusting the scales on both sides to prepare a coating film with a uniform thickness. After drying at 120° C. for 15 minutes, the release film was removed to obtain a single-layer resin film (11) with a thickness of 40 μm.

[Example 12] to [Example 20] Production of resin film (12) to resin film (20)
A single-layer resin film ( 12) to obtain a resin film (20).

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

[Comparative Example 11]
A transparent polyimide (thickness: 50 μm) was also subjected to the following tests.
[Comparative Example 12]
The following tests were similarly performed even when the resin film was not placed.

<Impact absorption test>
A chrome steel ball (model number: CR-3/4, material: chrome steel (SUJ-2), size: 3/4 inch, manufactured by AS ONE Corporation) was dropped from a height of 10 cm. A resin film sample was placed at the drop point, and SUS430 (thickness: 0.5 cm) was placed under it. A general-purpose piezoelectric load cell (model: 208C05, manufactured by PCB Piezotronics) was installed under SUS430, and the impact force applied to the resin film sample when dropped was measured using an oscilloscope (model number: DS-5107B, manufactured by Iwasaki Tsushinki Co., Ltd.). measured by A signal conditioner (model: 480C02, manufactured by PCB Piezotronics) was connected between the general-purpose piezoelectric load cell and the oscilloscope.
For the resin film sample, slide glass (product name: ASLAB, MICROSCOPE SLIDES, 25 mm × 75 mm, thickness: 1 mm, manufactured by AS ONE Co., Ltd.) was cut into a length of about 25 mm × 30 mm, and a resin film was placed on or under the glass. prepared each.

<Glass protection test>
The state of the glass after the impact absorption test was observed.
In addition, when the glass was broken, it was considered that part of the impact force contributed to the breakage of the glass, so it was not measured in the impact absorption test.

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

Test results:
From Tables 4 and 5, the glass is broken by a falling ball with only the glass, but the glass is protected not only when the resin films of Examples 11 to 20 are placed on the glass, but also when the film is placed below. It became clear that there is a function to
In addition, transparent polyimide broke the glass when the film was placed on the glass, but did not break when the film was placed underneath, so it protects the glass more than the resin films of Examples 11 to 20. It turned out to be less functional.

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

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

Formation of resin layer 13: preparation of laminated resin film (21) Further, polymer (21) (concentration: 42%) was cast onto resin layer 12, and an applicator (product name: No. 510 Baker film applicator, Co., Ltd.) was used. ) manufactured by Yasuda Seiki) to prepare a coating film with a uniform thickness. After drying at 120° C. for 15 minutes, a resin layer 13 was obtained which was a three-layer film (total film thickness: 100 μm) consisting of polymer (21)/polymer (22)/polymer (21). A laminated resin film (21) was obtained by removing the release film.

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

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

Formation of resin layer 16: Preparation of laminated resin film (22) Further, the polymer (22) (concentration: 20%, solvent: DMAc) synthesized in Production Example 22 was distilled under reduced pressure to remove the solvent to give a concentration of 46%. The resulting solution was applied onto the resin layer 15, and an applicator (product name: No. 510 Baker-type film applicator, manufactured by Yasuda Seiki Co., Ltd.) was used to prepare a coating film having a uniform thickness. After drying at 120° C. for 15 minutes, a resin layer 16 was obtained which was a three-layer film (total film thickness: 100 μm) consisting of polymer (22)/polymer (21)/polymer (22). A laminated resin film (22) was obtained by removing the release film.

[Example 23] Production of single-layer resin film (23) using polymer (21) Polymer (21) (concentration: 20%, solvent: DMAc) synthesized in Production Example 21 was was distilled off and a solution having a concentration of 50% was prepared in advance and used. A release film was used as the substrate. The polymer (21) (concentration 50%) was cast onto the substrate, and an applicator (product name: No. 510 Baker film applicator, manufactured by Yasuda Seiki Co., Ltd.) was used to prepare a coating film with a uniform thickness. . After drying at 120° C. for 15 minutes, the release film was removed to obtain a single-layer resin film (23) with a thickness of 100 μm.

[Example 24] Production of single-layer resin film (24) using polymer (22) By the same method as in Example 23, except that the polymer (22) was used instead of the polymer (21). , a single-layer resin film (24) having a thickness of 100 μm was obtained.

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

[Example 26] Production of laminated resin film (26) using polymer (22) A laminated resin film (26) having a total film thickness of 400 μm was obtained.

Table 6 shows the properties and film thickness of the obtained laminated and single-layer resin films.

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

<Impact absorption test>
A shock absorption test was conducted under the same conditions as in Examples 11 to 20, except that a chrome steel ball was dropped from a height of 30 cm and the glass was removed from the resin film sample to avoid the effects of glass breakage. .
<Glass protection test>
A resin film was placed under the glass on the SUS vat, and a chrome ball was dropped using an acrylic pipe with a height of 50 cm. tested.

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

Test results:
Examples 21 to 24 had smaller impact force than Comparative Example 13 in all cases. Moreover, the laminated film of Example 21 had the smallest impact force.

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

Test results:
In both Examples 25 and 26, the impact force was smaller than that in Comparative Example 14. It was found 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 this specification are individually identified and incorporated by reference, and the entire contents of each are set forth herein. To the same extent, incorporated herein by reference.

The use of nouns and similar denoting terms used in connection with the description of the present invention (especially in connection with the claims below) unless otherwise indicated herein or clearly contradicted by context. , to cover both the singular and the plural. The phrases “comprising,” “having,” “including,” and “including” are to be construed as open-ended terms (ie meaning “including but not limited to”) unless stated otherwise. Recitation of numerical ranges herein, unless otherwise indicated herein, is intended merely to serve as a shorthand method for referring individually to each value falling within the range. , and each value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. Any examples or exemplary language (e.g., "such as") used herein are intended merely to better illustrate the invention and constitute limitations on the scope of the invention, unless otherwise claimed. 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 this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those preferred embodiments will become apparent to those of ordinary skill in the art upon reading the above description. The inventors anticipate that skilled artisans will apply such variations as appropriate, and anticipate that the invention will be practiced otherwise than as specifically described herein. . Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

The block copolymer of the present invention is not only useful 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 its main chain. , is also extremely useful as a reactive oligomer.

Claims (16)

It is a polyaddition copolymer of Alternating Copolymer 1 below and Alternating Copolymer 2 below, which contains a repeating unit represented by formula (3), has a weight average molecular weight of 5,000 to 1,000,000, and has a terminal is either optionally capped —NH ₂ —OH or —NCO,
block copolymer.
- [(alternating copolymer 1) - (alternating copolymer 2)] - formula (3)
Alternating copolymer 1:
A polyaddition copolymer of a diisocyanate compound <A> and a diamine compound <B>, which has the formula (1)
-[(A)-(B)]- Formula (1)
A polyurea-based alternating copolymer having a repeating unit represented by and having a weight average molecular weight of 500 to 300,000 and both ends being —NH ₂ or —NCO;
Alternating copolymer 2:
A polyaddition copolymer of a diisocyanate compound <A> and a diamine compound <C ¹ >, represented by formula (2-1)
-[(A)-(C ¹ )]- Formula (2-1)
Polyurea-based alternating copolymer 2-1 containing repeating units represented by, having a weight average molecular weight of 500 to 300,000, and having -NCO or -NH ₂ at both ends,
and a polyaddition copolymer of a diisocyanate compound <A> and a diol compound <C ² >, which has the formula (2-2)
-[(A)-(C ² )]- Formula (2-2)
Polyurethane-based alternating copolymer 2-2 containing repeating units represented by and 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 at least one aliphatic isocyanate structural unit independently having a cyclic structure in the molecule;
(B) are each independently at least one structural unit selected from aromatic diamines, aromatic diamines having an ether bond, and aliphatic diamines having a cyclic skeleton;
(C ¹ ) is at least one structural unit selected from diamines having a siloxane skeleton;
(C ² ) represents at least one structural unit selected from diols having a siloxane skeleton.
provided that when both terminals of alternating copolymer 1 are —NCO, both terminals 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,
A block copolymer according to claim 1 . Both ends of alternating copolymer 1 are _-NH2 , and both ends of alternating copolymer 2 are -NCO,
A block copolymer according to claim 1 . Alternating copolymer 2 is polyurea-based alternating copolymer 2-1,
The block copolymer according to any one of claims 1-3. Alternating copolymer 2 is a polyurethane-based alternating copolymer 2-2,
The block copolymer according to any one of claims 1-3. The diisocyanate compound <A> is a compound represented by the following formulas (I) to (X),
In formulas (I) to (X) below, R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or alkyl having 1 to 7 carbon atoms,
each X is independently an 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 1-5.

The block copolymer according to any one of claims 1 to 6;
a solvent that dissolves the block copolymer;
Resin composition. The solvent includes propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, 4-methyl - including at least one of 2-pentanone, N,N-dimethylpropionamide, tetramethylurea, dimethylsulfoxide;
The resin composition according to claim 7. Containing a solid content obtained by removing the solvent from the resin composition according to claim 7 or claim 8,
coating. Formed from the solid content obtained by removing the solvent from the resin composition according to claim 7 or claim 8,
resin film. At least two layers of resin films formed from the solid content obtained by removing the solvent from the resin composition according to claim 7 or claim 8,
resin film. A resin film (H) formed by removing the solvent from the resin composition according to claim 7 or 8, wherein the block copolymer is the block copolymer according to claim 4. is a resin film (H);
A resin film (S) formed by removing the solvent from the resin composition according to claim 11, wherein the block copolymer is the block copolymer according to claim 5. comprising a film (S);
resin film. 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. 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. The resin film according to any one of claims 10 to 14;
OLED element. an OLED device according to claim 15;
Luminescent device.

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