JPWO2019049982A1 - Polyurea-based alternating copolymer, resin composition, coating film, resin film, OLED element, light emitting device, and method for producing polyurea-based alternating copolymer - Google Patents

Abstract

An object of the present invention is a reactive intermediate that has excellent transparency and heat resistance and is soluble in a general-purpose organic solvent, so that various functional groups can be introduced in a solution reaction. It is an object of the present invention to provide a novel alternating copolymer having a urea bond in the molecule, and a method for producing the same, which is also useful. The present invention is a polyurea alternating copolymer of a diisocyanate compound <A> and a diamine compound <B>, which comprises a repeating unit represented by the following formula (1) and has a weight average molecular weight of 5 to 300,000. Due to a polyurea-based alternating copolymer. -[(A)-(B)]-Formula (1) (In the formula, (A) is at least one type of aliphatic diisocyanate structural unit having a cyclic structure in the molecule, and (B) is independent of each other. At least one selected from structural units of aliphatic diamines, aromatic diamines, diamines having an ether bond, and diamines having a siloxane skeleton.)

Description

The present invention relates to a novel urea-based copolymer, which is useful as a starting material for a highly elastic recovery material, and a method for producing the same, which is intended for flexible devices in the field of electronic information materials. Furthermore, the present invention relates to materials that can be laterally applied to various applications such as automobiles, building materials, and life sciences.

In recent years, LCD (liquid crystal display) terminals that are portable and can be used outdoors have been remarkably spread, and examples include smartphones, mobile terminals typified by PND (personal navigation device), and wearable displays typified by Google Glass. As.
With the practical use of organic EL displays, there has been a demand for further weight reduction, and a method of switching some of the members from glass or thin film glass to plastic has been adopted. However, while thin-film glass has excellent heat resistance, it is extremely fragile, and plastics (especially PET, PC, PMMA, cycloolefin, etc.) have the characteristics of being lightweight and highly transparent, but they also have heat resistance and mechanical properties. However, there is a need for the development of new functional plastics.

The polyurea resin (polyurea resin) is a polymer compound having a urea bond formed in the skeleton by a chemical reaction between an isocyanate and an amino group. It is a resin with excellent mechanical strength and heat resistance, and since it does not hydrolyze, it has the characteristics of excellent water resistance, corrosion resistance, and chemical resistance.
Patent Document 1 discloses various rolls such as calender rolls used for papermaking, woven fabrics, magnetic tapes, casters and other general molding resins having a high hardness and toughness, and a new poly excellent in heat resistance. Urea resins are disclosed (paragraph 0001). However, this technique relates to a general molding resin that is used by being poured into a mold, and was not supposed to be applied to a film-shaped mobile terminal or the like in terms of handling and the like.
On the other hand, in Patent Document 2, the handling property is good, sagging at the time of coating can be prevented, and the coating work time can be sufficiently secured, and touch drying is possible within several hours. There is disclosed a polyurea resin composition having excellent coating physical properties after curing (paragraph 0008). However, since this technique relates to a two-component coating material/adhesive of a polyurea resin composition that is used by mixing an isocyanate component and an amine component, it is necessary to consider the curing time after mixing, and to improve the handling property. It was inferior.
Ordinary polyurea resin has excellent properties such as heat resistance and mechanical strength, but its use is limited because the reactivity of the isocyanate component and amine component is high and the cured product is insoluble in general-purpose organic solvents. Therefore, it was difficult to apply it to the field of electronic information materials, which requires precise coating.

JP-A-5-194695 JP-A-11-130834

The purpose of the present invention is to provide a reactive intermediate which is capable of introducing various functional groups in a solution reaction, since it has excellent transparency and heat resistance and is soluble in a general-purpose organic solvent. Another object of the present invention is to provide a novel alternating copolymer having a urea bond in the molecule and a method for producing the same.
Furthermore, since the novel alternating copolymer of the present invention has an amine or an isocyanate at the molecular end and a urea in the molecule, for example, a (meth)acrylate having an isocyanate group or a (meth)acrylate having an epoxy group is used. Is possible, and the vinyl functional group can be easily introduced.

The present inventor has conducted extensive studies to achieve the above object,
A copolymer obtained by subjecting a diisocyanate compound <A> and a diamine compound <B> to a polyaddition reaction,
An aliphatic diisocyanate compound having a cyclic structure in the molecule,
The present invention has been completed by finding a polyurea-based alternating copolymer comprising at least one diamine compound selected from an aliphatic diamine, an aromatic diamine, a diamine having an ether bond, and a diamine having a siloxane skeleton, and a method for producing the same. Came to do.
Examples of aspects of the invention are provided below.

［３］ 前記ジアミン化合物＜Ｂ＞が、直鎖状脂肪族ジアミン、エーテル結合を有する脂肪族ジアミンおよびシロキサン骨格を有するジアミンから選ばれる少なくとも１種であることを特徴とする、［１］または［２］に記載のポリウレア系交互共重合体。
［４］ 前記ジアミン化合物＜Ｂ＞が、芳香族ジアミン、エーテル結合を有する芳香族ジアミン、および環状骨格を有する脂肪族ジアミンから選ばれる少なくとも１種であることを特徴とする、［１］または［２］に記載のポリウレア系交互共重合体。
［５］ 末端が末端封止されていてもよい−ＮＨ_２または−ＮＣＯのいずれかである、［１］〜［４］に記載のポリウレア系交互共重合体。
［６］ ジイソシアネート化合物＜Ａ＞のモル数をｎ１、ジアミン化合物＜Ｂ＞のモル数をｎ２としたとき、それぞれのモル数が、１．０６≦ｎ２／ｎ１≦１．９の関係になるように調整することにより、両末端が末端封止されていてもよい−ＮＨ_２であることを特徴とする、［１］〜［５］のいずれかに記載のポリウレア交互共重合体。
［７］ ジイソシアネート化合物＜Ａ＞のモル数をｎ１、ジアミン化合物＜Ｂ＞のモル数をｎ２としたとき、それぞれのモル数が、１．０６≦ｎ１／ｎ２≦１．９の関係になるように調整することにより、両末端が末端封止されていてもよい−ＮＣＯであることを特徴とする、［１］〜［５］のいずれかに記載のポリウレア交互共重合体。
［８］ ［１］〜［７］のいずれかに記載のポリウレア交互共重合体と；前記ポリウレア交互共重合体を溶解する溶媒と；を含む、樹脂組成物。
［９］ 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、［８］に記載の樹脂組成物。
［１０］ ［８］または［９］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。
［１１］ ［８］または［９］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。
［１２］ ［８］または［９］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。
［１３］ ［１１］または［１２］に記載の樹脂フィルム；を備える、ＯＬＥＤ素子。
［１４］ ［１３］に記載のＯＬＥＤ素子；を備える、発光装置。
［１５］ ［１］〜［７］のいずれかに記載の、前記ジイソシアネート化合物＜Ａ＞と前記ジアミン化合物＜Ｂ＞を、１種以上の有機溶剤に溶解させ、溶液重合により共重合体を得ることを特徴とする、ポリウレア系交互共重合体の製造方法。[1] A polyaddition alternating copolymer of a diisocyanate compound <A> and a diamine compound <B>, which contains a repeating unit represented by the following formula (1) and has a weight average molecular weight of 500 to 300,000. Alternating polyurea copolymer.

-[(A)-(B)]- Formula (1)
(In the formula, (A) represents at least one kind of an aliphatic diisocyanate structural unit having a cyclic structure in the molecule,
(B) is at least one selected independently from the structural units of aliphatic diamine, aromatic diamine, diamine having an ether bond, and diamine having a siloxane skeleton. )
[2] The diisocyanate compound <A> is a compound represented by the following formulas (I) to (X),
In the following formulas (I) to (X), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or alkyl having 1 to 7 carbon atoms,
X is independently alkylene having 1 to 7 carbon atoms,
Y are each independently oxygen, sulfur, a straight chain or branched alkylene having a carbon number of _{1~7, -C (CF 3) 2} - or -SO ₂ - is,
The polyurea alternating copolymer according to [1].

[3] The above-mentioned diamine compound <B> is at least one kind selected from a linear aliphatic diamine, an aliphatic diamine having an ether bond and a diamine having a siloxane skeleton, [1] or [1] 2] The polyurea-based alternating copolymer according to [2].
[4] [1] or [1], wherein the diamine compound <B> is at least one selected from an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton. 2] The polyurea-based alternating copolymer according to [2].
[5] The polyurea-based alternating copolymer according to [1] to [4], wherein the end is either -NH ₂ or -NCO which may be end-capped.
[6] 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 have a relationship of 1.06≦n2/n1≦1.9. The alternating polyurea copolymer according to any one of [1] to [5], wherein both ends are -NH ₂ which may be end-capped.
[7] 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 have a relationship of 1.06≦n1/n2≦1.9. The polyurea alternating copolymer according to any one of [1] to [5], which is -NCO in which both ends may be end-capped.
[8] A resin composition containing the polyurea alternating copolymer according to any one of [1] to [7]; and a solvent that dissolves the polyurea alternating copolymer.
[9] The solvent is propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, The resin composition according to [8], which contains at least one of 4-methyl-2-pentanone, N,N-dimethylpropionamide, tetramethylurea, and dimethylsulfoxide.
[10] A coating film containing a solid content obtained by removing the solvent from the resin composition according to [8] or [9].
[11] A resin film formed from a solid content obtained by removing the solvent from the resin composition according to [8] or [9].
[12] 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 [8] or [9].
[13] An OLED element comprising: the resin film according to [11] or [12].
[14] A light emitting device comprising: the OLED element according to [13].
[15] The diisocyanate compound <A> and the diamine compound <B> according to any one of [1] to [7] are dissolved in one or more organic solvents to obtain a copolymer by solution polymerization. A method for producing a polyurea-based alternating copolymer, comprising:

The present invention relates to a new urea-based copolymer and a method for producing the same. High transparency, heat resistance, or mechanical properties of the obtained copolymer can be arbitrarily controlled by selecting appropriate diisocyanates and diamine compounds. Further, by changing the charged composition of the compound, not only a copolymer having an arbitrary molecular weight can be obtained, but it is also possible to have amino groups or isocyanate groups at both ends, making it a general-purpose organic solvent. Very useful as a soluble reactive oligomer.

It is a photograph after the test of the glass protection test of Example 11(a). It is a photograph after the test of the glass protection test of Example 11(b). It is a photograph after the test of the glass protection test of Example 12(a). It is a photograph after the test of the glass protection test of Example 12(b). It is a photograph after the test of the glass protection test of Comparative Example 11(a). It is a photograph after the test of the glass protection test of Comparative Example 11(b). It is a photograph after the test of the glass protection test of Comparative Example 12 (a) and (b).

This application is based on Japanese Patent Application No. 2017-173496 filed on September 8, 2017 and Japanese Patent Application No. 2018-151547 filed on August 10, 2018 in Japan, the content of which is the present application. Form part of it. The present invention will be more fully understood from the detailed description below. 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 the preferred embodiments of the present invention and are described only for the purpose of description. From this detailed description, various changes and modifications will be apparent to those skilled in the art within the spirit and scope of the present invention. The applicant has no intention of presenting any of the described embodiments to the public, and any modifications or alternatives that may not be literally included in the scope of the claims shall be considered under the doctrine of equivalents. As part of the invention.

Hereinafter, the polyurea-based alternating copolymer according to the present invention, the method for producing the polyurea-based alternating copolymer, and their applications will be described in detail. However, the present invention is not limited to the embodiments described below.

1 Polyurea-based alternating copolymer The polyurea-based alternating copolymer of the present invention is a polyaddition alternating copolymer of a diisocyanate compound <A> and a diamine compound <B> and is represented by the following formula (1). It is a polyurea-based alternating copolymer containing a repeating unit and having a weight average molecular weight of 500 to 300,000.

-[(A)-(B)]- Formula (1)
(In the formula, (A) represents at least one kind of an aliphatic diisocyanate structural unit having a cyclic structure in the molecule,
(B) is at least one selected independently from the structural units of aliphatic diamine, aromatic diamine, diamine having an ether bond, and diamine having a siloxane skeleton. )

The polyurea-based alternating copolymer is obtained by polyadding the diisocyanate compound <A> and the diamine compound <B>. The diisocyanate compound <A> and the diamine compound <B> correspond to the structural unit (A) and the structural unit (B) in the alternating copolymer, respectively. The binding site between the structural units (A) and (B) is a urea structure (-NH-CO-NH-).

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

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 carbon of an aliphatic ring. ..

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

Further, 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, but is disclosed in, for example, JP-A-2016-199694. The compound which is mentioned is mentioned.

Aliphatic diisocyanate 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-isocyanate-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-diisocyanate decalin, 2,7- Diisocyanate decalin, 1,4-diisocyanate decalin, 2,6-diisocyanate decalin, dicyclohexyl sulfide-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 independently selected from an aliphatic diamine, an aromatic diamine, a diamine having an ether bond, and a diamine having a siloxane skeleton. Not a thing.

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 a linear or branched aliphatic hydrocarbon or carbon of an aliphatic ring. .. The aromatic diamine of the present invention is a compound in which an amino group is directly bonded to carbon of an aromatic ring and which has two amino groups in the molecule.

Particularly, the diamine compound <B> that can be used for imparting high transparency is a diamine compound selected from a linear aliphatic diamine, an aliphatic diamine having an ether bond, and a diamine having a siloxane skeleton, Specific examples 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, a diamine compound having a siloxane skeleton represented by the following formula (XI), and the like can be given.

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

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

Particularly, the diamine compound <B> that can be used for imparting high heat resistance is a diamine compound selected from aromatic diamine, aromatic diamine having an ether bond, and aliphatic diamine 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 preferable in terms of heat resistance and mechanical properties, and 4,4′-diaminodiphenylmethane and 2,2-bis[4-(4-aminophenoxy)phenyl] Propane can be used particularly preferably.

The diamine compound <B> that can be used in the present invention is not particularly limited as long as it is a diamine compound selected from aliphatic diamine, aromatic diamine, diamine having an ether bond, and diamine having a siloxane skeleton. For example, the compounds disclosed in JP-A-2014-65921 can be 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, as the diamine compound <B> that can be used to impart high transparency, for example, a linear aliphatic diamine represented by the formula (XII-1) to (XII-3), a formula (XII- 4) to (XII-8) include aliphatic diamines having an ether bond.

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

As the aliphatic diamine having an ether bond represented by the formula (XII-8), for example, trade name: Jeffamine D-230 (a=0, b=0, c=2, manufactured by Mitsui Fine Chemicals, Inc.) is used. -3), D-400 (a=0, b=0, c=5-6), D-2000 (a=0, b=0, c=about 33), D-4000, etc. Jeffermin D series Jeffamine ED-600 (b=9.0, a+c=3.6), ED-900 (b=12.0, a+c=3.6), ED-2003 (b=38.7, a+c=6) . 0) etc. Jeffermin ED series; etc. can be used.

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

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

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

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

Examples thereof include aromatic diamines represented by formulas (XVII-1) to (XVII-4) and aromatic diamines having an ether bond 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 an ether bond represented by formulas (XVIII-8) to (XVIII-11).

Furthermore, specific examples of the diamine compound <B> that can be used in the present invention include aromatic diamines represented by formulas (XIX-1) to (XIX-11).

In formulas (XIX-1), (XIX-2), (XIX-7) and (XIX-8), R ₂₀ is an organic group having 1 to 30 carbon atoms, and among these, R ₂₀ has 3 to 12 carbon atoms. Alkyl or alkoxy having 3 to 12 carbons is preferable, and alkyl having 5 to 12 carbons or alkoxy having 5 to 12 carbons is more preferable. In addition, in the above formulas (XIX-3) to (XIX-6) and (XIX-9) to (XIX-11), R ₂₁ is an organic group having 1 to 30 carbon atoms. Alkyl having 10 to 10 or alkoxy having 1 to 10 carbons is preferable, and alkyl having 3 to 10 carbons or alkoxy having 3 to 10 carbons is more preferable.

Further, examples thereof include aromatic diamines represented by the formulas (XIX-12) to (XIX-17).

In formulas (XIX-12) to (XIX-15), R ₂₂ is an organic group having 1 to 30 carbon atoms, preferably alkyl having 4 to 16 carbon atoms, and more preferably alkyl having 6 to 16 carbon atoms. In formulas (XIX-16) and (XIX-17), R ₂₃ is an organic group having 1 to 30 carbon atoms, preferably alkyl having 6 to 20 carbons, and more preferably alkyl having 8 to 20 carbons.

Further, examples thereof include aromatic diamines represented by formulas (XIX-18) to (XIX-38).

The above formulas (XIX-18), (XIX-19), (XIX-22), (XIX-24), (XIX-25), (XIX-28), (XIX-30), (XIX-31), In (XIX-36) and (XIX-37), R ₂₄ is an organic group having 1 to 30 carbon atoms, preferably alkyl having 1 to 12 carbons and alkoxy having 1 to 12 carbons, and 3 to 12 carbons. And alkyl having 3 to 12 carbons are more preferable. Further, the above formulas (XIX-20), (XIX-21), (XIX-23), (XIX-26), (XIX-27), (XIX-29), (XIX-32) to (XIX-35). And (XIX-38), R ₂₅ is hydrogen, —F, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ . , C3-12 alkyl or C3-12 alkoxy is more preferred. In the above formulas (XIX-33) and (XIX-34), A is alkylene having 1 to 12 carbon atoms.

Further, examples thereof include aromatic diamines represented by the formulas (XIX-39) to (XIX-48).

Furthermore, specific examples of the diamine compound <B> that can be used in the present invention include aromatic diamines represented by formulas (XX-1) to (XX-4).

Furthermore, specific examples of the diamine compound <B> that can be used in the present invention include aromatic diamines represented by formulas (XXI-1) to (XXI-8).

Furthermore, specific examples of the diamine compound <B> that can be used in the present invention include aromatic diamines represented by formulas (XXII-1) to (XXII-9).

In the above formulas (XXII-1) to (XXII-3), R ₂₆ is preferably hydrogen or alkyl having 1 to 20 carbon atoms, and in the above formulas (XXII-4) to (XXII-9), R ₂₇ is hydrogen or Alkyl having 1 to 10 carbon atoms is preferable.

Furthermore, specific examples of the diamine compound <B> that can be used in the present invention include aromatic diamines represented by formulas (XXIII-1) to (XXIII-3).

In the formulas (XXIII-1) to (XXIII-3), R ₂₈ is alkyl having 2 to 30 carbon atoms, among these, alkyl having 6 to 20 carbon atoms is preferable, and R ₂₉ is hydrogen or 1 to 30 carbon atoms. Of these, and among these, hydrogen or alkyl having 1 to 10 carbon atoms is preferable.

In the present invention, the diamine can be used as the diamine compound <B>, but diamines other than these diamines can also be used. For example, a naphthalene-based diamine having a naphthalene structure, a fluorene-based diamine having a fluorene structure, an aromatic diamine represented by the following formulas (XXIV-1) to (XXIV-8), and the like can be used.

In the formula, R ₃₀ and R ₃₁ are independently alkyl having 3 to 20 carbons.

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

1.3 Other Diisocyanate Compounds The polyurea alternating copolymer of the present invention is not particularly limited as long as it contains a repeating unit represented by the following formula (1).

-[(A)-(B)]- Formula (1)
(In the formula, (A) represents at least one kind of an aliphatic diisocyanate structural unit having a cyclic structure in the molecule,
(B) is at least one selected independently from the structural units of aliphatic diamine, aromatic diamine, diamine having an ether bond, and diamine having a siloxane skeleton. )

The polyurea-based alternating copolymer of the present invention can be subjected to the alternating copolymerization by substituting a part of the diisocyanate compound <A> with another diisocyanate compound as long as the characteristics of the resulting alternating copolymer are not impaired.

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

Specific preferred examples of other diisocyanate compounds include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate. 2,4'-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 can be mentioned.

Further, other diisocyanate compounds include, for example, aliphatic diisocyanates, aromatic diisocyanates, sulfur-containing aliphatic diisocyanates, aliphatic sulfide-based diisocyanates, aromatic sulfide-based diisocyanates, and aliphatic diisocyanates disclosed in JP-A-2016-199694. Examples thereof include sulfone-based diisocyanate, aromatic sulfone-based diisocyanate, sulfonic acid ester-based diisocyanate, aromatic sulfonic acid amide-based diisocyanate, and sulfur-containing heterocyclic diisocyanate. Specific examples of these diisocyanate compounds include the following compounds.

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

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

Aliphatic diisocyanate; ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate , Butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-trimethylundecamethylene diisocyanate, 1,3,6-trimethylhexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane, bis(isocyanate ethyl)carbonate, bis(isocyanate ethyl) ether, 1, 4-butylene glycol dipropyl ether ω,ω'-diisocyanate, lysine diisocyanate methyl ester

Aromatic diisocyanates; xylylene diisocyanates (o-, m-, p-), tetrachloro-m-xylylene diisocyanate, 4-chloro-m-xylylene diisocyanate, 4,5-dichloro-m-xylylene diisocyanate, 2 , 3,5,6-Tetrabromo-p-xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, 4-ethyl-m-xylylene diisocyanate, 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, ethyl phenylene diisocyanate, isopropyl Phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate, tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate , Bibenzyl-4,4'-diisocyanate, bis(isocyanatophenyl)ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, phenylisocyanate methylisocyanate, phenylisocyanateethylisocyanate, tetrahydronaphthylenediisocyanate, 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, dibenzofurandiocyanate, carbazole diisocyanate, ethyl Carbazole diisocyanate , Dichlorocarbazole diisocyanate

Sulfur-containing aliphatic diisocyanate; thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone 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 (Isocyanate methylthio)methane, bis(isocyanatoethylthio)methane, bis(isocyanatoethylthio)ethane, bis(isocyanatomethylthio)ethane, 1,5-isocyanate 2-isocyanatomethyl-3-thiapentane

Aliphatic sulfide-based diisocyanate; bis[2-(isocyanatemethylthio)ethyl]sulfide, bis(isocyanatemethyl)sulfide, bis(isocyanatoethyl)sulfide, bis(isocyanatopropyl)sulfide, bis(isocyanatehexyl)sulfide, bis(isocyanatomethyl) ) Disulfide, bis(isocyanatoethyl) disulfide, bis(isocyanatopropyl) disulfide

Aromatic sulfide-based diisocyanate; diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzyl thioether, bis(4-isocyanate methylbenzene ) Sulfide, 4,4'-methoxybenzenethioethylene glycol-3,3'-diisocyanate, diphenyldisulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyldisulfide-5,5'-diisocyanate, 3 ,3'-Dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-Dimethyldiphenyldisulfide-6,6'-diisocyanate, 4,4'-Dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3 '-Dimethoxydiphenyldisulfide-4,4'-diisocyanate, 4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate

Aliphatic sulfone-based diisocyanates; bis(isocyanatomethyl) sulfone

Aromatic sulfone-based diisocyanate; diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzylidenesulfone-4,4'-diisocyanate, diphenylmethanesulfone-4,4'-diisocyanate, 4-methyldiphenylmethane Sulfone-2,4'-diisocyanate, 4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzylsulfone, 4,4'-dimethyldiphenylsulfone -3,3'-diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate, 4,4'-dimethoxybenzeneethylenedisulfone-3,3'-diisocyanate, 4,4'- Dichlorodiphenyl sulfone-3,3'-diisocyanate Sulfonic acid ester-based diisocyanate; 4-methyl-3-isocyanate benzenesulfonyl-4'-isocyanate phenol ester, 4-methoxy-3-isocyanate benzenesulfonyl-4'-isocyanate pheno- Luster

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

Sulfur-containing heterocyclic diisocyanate; thiophene-2,5-diisocyanate, thiophene-2,5-diisocyanate methyl, 1,4-dithiane-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanatemethyl, 1, 3-dithiolane-4,5-diisocyanate, 1,3-dithiolane-4,5-diisocyanate methyl, 1,3-dithiolane-2-methyl-4,5-diisocyanate methyl, 1,3-dithiolane-2,2- Diisocyanate ethyl, tetrahydrothiophene-2,5-diisocyanate, tetrahydrothiophene-2,5-diisocyanate methyl, tetrahydrothiophene-2,5-diisocyanate ethyl, tetrahydrothiophene-3,4-diisocyanate methyl, 2-(1,1-diisocyanate Methyl)thiophene, 3-(1,1-diisocyanate methyl)thiophene, 2-(2-thienylthio)-1,2-diisocyanate propane, 2-(3-thienylthio)-1,2-diisocyanate propane, 3-(2 -Thienyl)-1,5-diisocyanate-2,4-dithiapentane, 3-(3-thienyl)-1,5-diisocyanate-2,4-dithiapentane, 3-(2-thienylthio)-1,5-diisocyanate- 2,4-Dithiapentane, 3-(3-thienylthio)-1,5-diisocyanate-2,4-dithiapentane, 3-(2-thienylthiomethyl)-1,5-diisocyanate-2,4-dithiapentane, 3- (3-thienylthiomethyl)-1,5-diisocyanate-2,4-dithiapentane, 2,5-(diisocyanatemethyl)thiophene, 2,3-(diisocyanatemethyl)thiophene, 2,4-(diisocyanatemethyl)thiophene, 3,4-(diisocyanate methyl)thiophene, 2,5-(diisocyanate methylthio)thiophene, 2,3-(diisocyanate methylthio)thiophene, 2,4-(diisocyanate methylthio)thiophene, 3,4-(diisocyanate methylthio)thiophene

The diisocyanate compound is usually used for producing polyurea and polyurethane, but industrially it is produced by reacting phosgene with a corresponding diamine as a starting material. That is, the desired diisocyanate compound <A> and other diisocyanate compounds can be produced using the diamine compound <B> as a starting material.

Further, as the other diisocyanate compound, a blocked isocyanate compound having an isocyanate group protected can be used. The blocked isocyanate compound is a compound in which an isocyanate group (-NCO) is blocked by a thermally removable protective group, and can be obtained by reacting the isocyanate group of the isocyanate compound with a blocking agent.

As the blocking agent for the isocyanate compound, known compounds can be selected and used, and examples thereof include methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2- Alcohols such as ethoxyethanol and cyclohexanol, phenols such as phenol, o-nitrophenol, p-chlorophenol, o-cresol, m-cresol and p-cresol, lactams such as ε-caprolactam, acetone oxime and methyl ethyl ketone. Oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, benzophenone oxime, and other oximes, pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, and other pyrazoles, dodecanethiol, benzenethiol, and other thiols, malonic acid Examples thereof include active methylene compounds such as dimethyl, diethyl malonate, acetoacetic acid ester, malonic acid dinitrile, acetylacetone, methylenedisulfone, dibenzoylmethane, dipivaloylmethane, and acetonedicarboxylic acid diester.

Specific examples of the blocked isocyanate compound include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate and m-xylylene. Diisocyanate, p-xylylene diisocyanate, 2,4-tolylene dimer, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate), isophorone diisocyanate, (bicyclo[2 1.2.1!heptane-2,5-diyl)bismethylene diisocyanate, (bicyclo[2.2.1]heptane-2,6-diyl)bismethylene diisocyanate, 2β,5α-bis(isocyanate)norbornane, 2β, Blocked isocyanates in which the isocyanate group of 5β-bis(isocyanate) norbornane, 2β,6α-bis(isocyanate) norbornane, 2β,6β-bis(isocyanate) norbornane are protected with the above blocking agent can be mentioned.

As the blocked isocyanate compound, it is possible to use a commercially available one. For example, Asahi Kasei Chemicals Co., Ltd. trade name Duranate SBN-70D, TPA-B80E, TPA-B80X, 17B-60PX, MF-B60X, E402-B80T, ME20-B80S, MF-K60X, and hexamethylene diisocyanate such as K6000. (Hereinafter, also referred to as "HDI".) Blocked isocyanate, trade name Takenate B-882N of Mitsui Chemicals Polyurethane Company, trade name Takenate B-830, 4,4'-diphenylmethane diisocyanate which is a tolylene diisocyanate blocked isocyanate. Trade name Takenate B-815N, which is a net block isocyanate, and Takenate B-846N, which is a 1,3-bis(isocyanatomethyl)cyclohexane block isocyanate, and a toluene diisocyanate block isocyanate, product number Coronate manufactured by Tosoh Corporation. BI-301, Coronate 2507, Coronate 2554, Isophorone diisocyanate-based blocked isocyanate manufactured by Baxenden, product numbers 7950, 7951, 7990, Hexamethylene diisocyanate-based blocked isocyanate manufactured by Baxenden, product numbers 7960, 7961, 7982, 7991, 7992. And so on.

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

Alternatively, diisocyanate compounds that are commercially available as a mixture can be used. For example, the product name Coronate manufactured by Tosoh Corporation is a mixture of isomers of 2,4′-tolylene diisocyanate (2,4′-TDI) and 2,6′-tolylene diisocyanate (2,6′-TDI). However, the ratio of 2,4'-TDI/2,6'-TDI is 80/20, and the ratio of 2,4'-TDI/2,6'-TDI is 65/35. T-65 can be used.

In the present invention, part of the diisocyanate compound <A> can be replaced with another diisocyanate compound to obtain a polyurea alternating copolymer.
Other diisocyanate compounds can be used as long as the properties of the resulting alternating copolymer are not impaired. For example, the number of moles of diisocyanate compound <A> is n1, and the number of moles of diamine compound <B> is n2. At this time, 0 to 90 mol% of n1 can be replaced with another diisocyanate compound. The substitution can be carried out preferably in the range of 0 to 70 mol %, more preferably in the range of 0 to 50 mol %.

1.4 Weight average molecular weight In the present invention, a polyurea alternating copolymer having a weight average molecular weight of 500 to 300,000 can be preferably used. The polyurea alternating copolymer having a weight average molecular weight of 500 or more has good heat resistance and mechanical properties, and the polyurea alternating copolymer having a weight average molecular weight of 300,000 or less is soluble in a general-purpose organic solvent. Therefore, it has good handleability and is also useful as a reactive intermediate capable of introducing various functional groups by a solution reaction. Further, in the present invention, in order to further improve the solubility and handleability of the polyurea alternating copolymer in a solvent, the weight average molecular weight thereof is preferably 500 to 40,000, and 500 to 30,000. Is more preferable.

The weight average molecular weight of the polyurea alternating copolymer can be measured by a gel permeation chromatography (GPC) method. Specifically, the obtained polyurea alternating copolymer is mixed with tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) so that the concentration of the polyurea alternating copolymer is about 1% by weight. It can be determined by diluting, measuring by gel permeation chromatography (GPC) method under the following conditions, and converting into polystyrene.
<GPC>
Equipment: JASCO Corporation LC-2000Plus series (detector: differential refractometer)
Solvent: THF/DMF=1/1 (v/v)
Flow rate: 0.5 ml/min
Column temperature: 40 ℃
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

Polyurea alternating copolymer of 1.5-terminus present invention, the terminal may be either -NH ₂ or -NCO, but polyurea alternating copolymer both ends is -NH ₂ or both ends, A polyurea-based alternating copolymer in which is —NCO can be particularly preferably used. Such a polyurea-based alternating copolymer is chemically stable, and particularly when it is used as a reactive intermediate, it can be preferably used because it leads to control of the reactive group to —NH ₂ or —NCO.

When the number of moles of the diisocyanate compound <A> is n1 and the number of moles of the diamine compound <B> is n2, for example, the polyurea alternating copolymer whose both ends are -NH ₂ has a number of moles of 1 each. It can be obtained by adjusting so as to have a relationship of 0.06≦n2/n1≦1.9, more preferably 1.1≦n2/n1≦1.8, further preferably 1.1≦n2/ n1≦1.6.
By excess number of moles of the diamine compound <B>, chemically stable, has a weight average molecular weight of the preferred range, both terminals can be obtained polyurea alternating copolymer is -NH _2.

When the number of moles of the diisocyanate compound <A> is n1 and the number of moles of the diamine compound <B> is n2, for example, the polyurea alternating copolymer having both ends of -NCO has a molar number of 1. It can be obtained by adjusting so as to satisfy the relationship of 06≦n1/n2≦1.9, more preferably 1.1≦n2/n1≦1.8, further preferably 1.1≦n2/n1. ≦1.6.
By making the number of moles of the diisocyanate compound <A> excessive, it is possible to obtain a polyurea alternating copolymer which is chemically stable and has a weight average molecular weight in a preferable range and whose both ends are -NCO.

1.6 When the end-capped polyurea alternating copolymer is not used as a reactive intermediate, it can be used by capping the end reactive group, —NH ₂ or —NCO.

If terminal reactive group is -NCO, -NH ₂ group as a terminal blocking agent, -OH group, -COOH group, the compound having a -SO ₂ H group can be used.

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

Specific examples of the compound having an —OH group that can be used as the terminal blocking agent include monoalcohol compounds having 1 to 18 carbon atoms. Examples of the monoalcohol compound having 1 to 18 carbon atoms include linear monools (methanol, ethanol, n-propanol, n-butanol, pentanol, hexanol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecanol). Decyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, etc.); monools having a branched chain (isopropanol, sec-, iso- or tert-butanol, neopentyl alcohol, 3-methyl-pentanol and 2-ethylhexanol) Etc.); monools having a cyclic group of 6 to 10 carbon atoms [aliphatic group-containing monools (cyclohexanol, etc.) and aromatic ring-containing monools (benzyl alcohol, etc.)]. Further, specific examples of the compound having an —OH group include polymer monools (polyester monool, polyether monool, polyether ester monool, etc.), cellosolves, and carbitols. Of these, linear monools are preferred. Specifically, it is methanol, ethanol, n-propanol, n-butanol or 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 urethane-forming catalyst such as dibutyltin dilaurate can be used as the reaction catalyst. Examples of the urethanization catalyst include various nitrogen-containing compounds such as N,N-dimethylaminoethyl ether, triethylamine, triethylenediamine, and N-methylmorpholine, potassium acetate, zinc stearate, and tin octylate. Examples thereof include metal salts, various organometallic compounds such as dibutyltin dilaurate, and chelate compounds such as zirconium tetraacetylacetonate.

If terminal reactive group is -NH _2, it can be used a compound having a -NCO group as a terminal blocking agent.

Specific examples of the compound having an -NCO group that can be used as the 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.

2 Method for producing polyurea alternating copolymer The method for producing a polyurea alternating copolymer of the present invention comprises dissolving the diisocyanate compound <A> and the diamine compound <B> in one or more organic solvents, It is characterized in that a copolymer is obtained by solution polymerization.

The reaction solvent used for dissolving the diisocyanate compound <A> and the diamine compound <B> to obtain a copolymer by solution polymerization is not particularly limited as long as a polyurea alternating copolymer can be synthesized. .. As the reaction solvent, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, 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 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 Le-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 It is preferable to use 2-pentanone, N,N-dimethylpropionamide, tetramethylurea or dimethylsulfoxide because the polyurea alternating copolymer has good solubility and can be uniformly polymerized.
These reaction solvents may be used alone or in combination of two or more. Furthermore, in addition to the above reaction solvent, other solvent can be mixed and used.

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

Further, the order of adding the reaction raw materials to the reaction system is not particularly limited. That is, the diisocyanate compound <A> and the diamine compound <B> are simultaneously added to the reaction solvent, the diamine compound <B> is dissolved in the reaction solvent, and then the diisocyanate compound <A> is added, and the diisocyanate compound <A , A diamine compound <B> is added to the reaction solvent, and any other method can be used.

3 Use of polyurea-based alternating copolymer The polyurea-based alternating copolymer of the present invention is used as a material for protecting an image display device from impact in the field of image display devices represented by liquid crystal displays, organic EL displays and the like. can do. For example, in a liquid crystal display, a film or a coating material may be provided on the front surface or the back surface of a cover glass or a cover film, or the front surface or the back surface of a polarizing plate. In organic EL displays, thinning and weight reduction have been advanced due to flexibility, and there is an extremely high need to protect elements from external force such as impact. Along with this, the polyurea-based alternating copolymer of the present invention is useful as a front surface or a back surface of a cover glass or a cover film, a front surface or a back surface of a polarizing plate, a back film installed on an element body, or a coating material. It can also be used as a material inside the element such as a fill material, a sealing material, a dam material, a buffer material, and a flattening film.

In the automobile field, it is also useful as a material for protecting the exterior and interior of automobiles from impact. For example, the external coating may be a paint protection film or a coating material for protecting the external coating from scratches and the like. Taking advantage of the excellent impact absorption property of the polyurea alternating copolymer, it may be used as a film or coating material to be installed in an intermediate film of a laminated glass for automobiles, a glazing, a rear window, a rearview mirror, a sensor or the like.

Polyurea and polyurethane-based materials also have potential for use as biocompatible materials. It is also expected to be applied to medical devices that require blood compatibility, such as dialysis membrane that is made into a filter by spinning by spinning such as electrospinning, hollow fiber such as artificial heart lung, coating for drip needle that is embedded in the body for a long time. it can.

In the field of building materials, it may be used as a film or coating material to prevent the window glass from scattering, for example, to prevent the window glass of a high-rise building from being destroyed, scattered, and dropped in the event of an earthquake or earthquake. It may be used to prevent the glass from breaking. Polyurea is known to have enhanced impact resistance by coating structural buildings, such as concrete and block walls, and is also used as a coating material to prevent structural buildings from collapsing in the event of terrorism or an earthquake or earthquake. Good.

4 Resin composition The resin composition of the present invention is a composition containing the polyurea-based alternating copolymer; and a solvent that dissolves the alternating copolymer.
The solvent used in the resin composition of the present invention is not particularly limited as long as it can dissolve the polyurea alternating copolymer. For example, the reaction solvent used in the production of the polyurea alternating copolymer can be used as it is, or another solvent can be further added and used as a mixed solvent.
Alternatively, the polyurea alternating copolymer may be isolated as a solid and then redissolved in a desired solvent for use. As a method for isolating the polyurea-based alternating copolymer, a solution containing the polyurea-based alternating copolymer and a reaction solvent is poured into a poor solvent for the polyurea-based alternating copolymer such as methanol, ethanol, and isopropyl ether. A method of precipitating the polyurea-based alternating copolymer and separating it by filtration, washing, drying and the like can be mentioned. By performing such an operation, the catalyst used for producing the polyurea alternating copolymer can be removed.
Particularly preferred solvents are propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, 4 -Methyl-2-pentanone, N,N-dimethylpropionamide, tetramethylurea and dimethylsulfoxide may be mentioned. These solvents may be used alone or in combination of two or more.

The concentration of the polyurea-based alternating 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 method of forming the coating film, the thickness of the resin film, and the like. For example, the viscosity of the resin composition of the present invention at 25° C. may be in the range of 1 to 100,000 mPa·s, preferably in the range of 10 to 50,000 mPa·s before use.

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

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

As an ultraviolet absorber, ADEKA Corporation Adeka Stab LA-46, Adeka Stab LA-77Y, Adeka Stab LA-63P, Adeka Stab LA-72, Adeka Stab LA-32, BASF Corporation Tinuvin 479, Tinuvin 292, Tinuvin 123, Tinuvin. 384-2, Tinuvin 400 and the like.

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

Examples of the light stabilizer (HALS) include TINUVIN (registered trademark) 5100 (neutral type 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), TINUVIN 152 (Compound name: 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2, 6,6-Tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine), TINUVIN 144 (Compound name: bis(1,2,2,6,6-) Pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate), TINUVIN123 (Compound name: Decanedioic acid, Bis(2,2,2) Reaction product of 6,6-tetramethyl-1-(octyloxy)-4piperidinyl)ester (in the presence of 1,1-dimethylethylhydroperoxide and octane)), TINUVIN111FDL (about 50%, TINUVIN622, compound name: (Butanedioic acid polymer (4-hydroxy-2,2,6,6-tetramethylpiperidinyl-yl)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 ADEKA STAB LA series manufactured by ADEKA CORPORATION, and specifically, LA-52 ((5)-6116), LA-57 ((5)-5555), LA-62 ((5). -5711) and LA-67 ((5)-5755). The numbers in parentheses are the existing chemical substance numbers stipulated by the Act on Chemical Substances Examination and Regulation of Manufacturing 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, the content 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 sensitizer, polymerization inhibitor, wax, plasticizer, leveling agent, surfactant, dispersant, defoaming agent, wettability improver, antistatic agent, curing aid, It is possible to mix various additives such as an additive imparting antifouling properties and low friction properties, an additive imparting scratch resistance, a heat stabilizer, a flame retardant, and a release agent.

5 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 a structure by a method such as coating, printing or casting and then removing the solvent. The removing method may be drying, for example, and the drying method is not particularly limited. Examples include heating (hot air) drying, vacuum drying, steam drying, barrel drying, spin drying, suction drying and the like.
The drying method or the drying conditions may be appropriately selected depending on the type of solvent of the resin composition, the thickness and shape of the coating film, and the like. For example, in the case of heat drying, heat treatment using an air circulating constant temperature oven, a heater using microwaves or far infrared rays, a hot plate and the like can be mentioned. The drying conditions are not particularly limited as long as the solvent evaporates, but for example, the drying temperature may be 40 to 250° C. and the drying time may be 1 minute to 24 hours. The heating may be performed in two steps, and if necessary, the heating and drying may be performed under a nitrogen atmosphere or under reduced pressure.
The shape of the coating film from which the solvent has been removed may be determined in accordance with the use described in "Use of polyurea-based alternating copolymer". Alternatively, the solvent may be distilled off after applying the resin composition to a desired portion.
The coating film of the present invention is preferable because it provides a flat coating film.

6 Resin Film The resin film of the present invention is one in which the solid content obtained by removing the solvent from the resin composition of the present invention is formed into a film. For example, it can be produced by the steps of coating, drying and peeling the resin composition. The resin film may be used as a single layer, or may be used as a film in which a plurality of layers are laminated by repeating coating and drying.

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

The formation of the resin film is not particularly limited as long as it is a method capable of producing a thin film. A wet coating method (application method) other than the method using the applicator used in the examples may be used. By using a coating method, excellent surface smoothness can be obtained. Among the coating methods, a spin coating method and a bar coating method, which are simple and can form a uniform film when a small amount is prepared, can be mentioned. In the case of roll-to-roll where productivity is important, gravure coating method, die coating method, reverse coating method, roll coating method, slit coating method, dipping method, spray coating method, kiss coating method, reverse kiss coating method, air A knife coating method, a curtain coating method, a rod coating method, an inkjet method and the like can be mentioned. Further, a method using various printing devices such as a relief printing method, an intaglio printing method, a lithographic printing method and a stencil printing method can be mentioned. It may be appropriately selected from these methods depending on the required thickness, viscosity, curing conditions and the like.
The resin film of the present invention is preferable because it becomes a flat resin film. Further, in the case of a plurality of layers, the shock absorption can be further enhanced by combining resin films having different strengths.

7 OLED element The OLED element of the present invention comprises the resin film of the present invention. The OLED device may be either rigid or flexible type. Due to the excellent flexibility of the resin film, it is more suitable for flexible type devices.
Further, since the resin film of the present invention has excellent transparency and heat resistance, it is used as a transparent substrate in a bottom emission type flexible OLED element instead of a conventional glass substrate or polyethylene naphthalate (PEN) film substrate. be able to. Alternatively, it can be laminated on a conventional substrate or below the substrate and used as a shock absorbing film.
In the top emission type flexible OLED element, it can be used as a sealing film instead of the sealing glass. Alternatively, it may be laminated on or below a 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 resin has excellent properties such as heat resistance and mechanical strength, but its use is limited because the reactivity of the isocyanate component and amine component is high and the cured product is insoluble in general-purpose organic solvents. Therefore, it was difficult to apply it to the field of electronic information materials, which requires precise coating.
However, since it becomes possible to synthesize a polyurea resin soluble in a general-purpose organic solvent according to the present invention, it is possible to apply the resin composition to a desired place by drying and drying, and it is possible to apply the electronic information field. It has become possible.
Since the OLED element of the present invention is provided with a layer that absorbs impact, damage to the OLED element can be prevented.

8 Light Emitting Device The light emitting device of the present invention includes the OLED element of the present invention. Examples of the light emitting device include an organic EL display, particularly a flexible organic EL display, organic EL lighting, and particularly a flexible organic EL lighting.
The organic EL display is not particularly limited as long as it has the OLED element of the present invention. For example, a television, a personal digital assistant, a wearable system, a vehicle-mounted display, a digital signage, etc. can be mentioned.
Since the light emitting device of the present invention is provided with the layer that absorbs impact, it is possible to prevent the failure of the light emitting device due to the damage of the OLED element.

The present invention will be described more specifically with reference to 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)
DDM: 4,4'-diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.)
BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane (manufactured by Wakayama Seika Kogyo Co., Ltd.)
HXDA: 1,3-bis(aminomethyl)cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.)
HXDI: 1,3-bis(isocyanatomethyl)cyclohexane (Mitsui Chemicals, Inc., product name; Takenate 600)
HDI: Hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)
MDI: 4,4'-diphenylmethane diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)
DGBE: Diethylene glycol bis(3-aminopropyl) ether (manufactured by Tokyo Chemical Industry Co., Ltd.)
DMAc: N,N-dimethylacetamide (Kanto Chemical Co., Inc., dehydration)
THF: Tetrahydrofuran (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.)
NMP: N-methyl-2-pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.)
MIBK: 4-methyl-2-pentanone (manufactured by Tokyo Chemical Industry Co., Ltd.)
Solmix AP-1: Ethanol, 2-propanol, methanol, water mixture (Nippon Alcohol Sales Co., Ltd.)
Silaplane FM3311: α,ω-(3-aminopropyl)polydimethylsiloxane (manufactured by JNC)
Mw: Weight average molecular weight PDI (Mw/Mn): Molecular weight distribution index

Next, analysis conditions in production examples and examples will be shown.
<GPC>
Device: LC-2000Plus series manufactured by JASCO Corporation (detector: differential refractometer)
Solvent: THF/DMF=1/1 (v/v)
Flow rate: 0.5 ml/min
Column temperature: 40°C
Column used: Showa Denko KK, Asahipak GF-1G 7B (guard column) + Asahipak GF-7M HQ, exclusion limit molecular weight (PEG) = 10,000,000)
Standard sample for calibration curve: PSt
<TG/DTA>
Device: TG/DTA6200 (manufactured by SII Nanotechnology Inc.)
Temperature rising rate: 10°C/min
Measurement temperature: 50 to 400°C
Analysis: 5% weight loss temperature; Td ₅
<DSC>
Device: Diamond-DSC (manufactured by Perkin Elmer)
Temperature rising rate: 100°C/min
Measurement temperature: 20 to 200°C
Analysis: Midpoint glass transition temperature; Tmg (JIS K7121 compliant)
<Total light transmittance, haze>
Device: Haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.)
Analysis: According to JIS K7361

Example 1 Synthesis of Copolymer (1)/Synthesis of HXDI-DDM (1:1.2) Copolymer A 200 mL three-necked flask equipped with a reflux condenser, a temperature system and a dropping funnel under a nitrogen atmosphere. HXDI (2.25 g) and DMAc (47.5 g) were introduced into. It heated at 120 degreeC using the oil bath. Then, a solution in which DDM (2.75 g) was dissolved in DMAc (47.5 g) was introduced all at once with a syringe to start the reaction (HXDI-DDM=1:1.2). Then, while maintaining at 120° C., the mixture was stirred for 6 hours to obtain a transparent reaction liquid. The Mw determined by GPC analysis of the reaction solution was 4,900, and the PDI was 2.3.
Furthermore, 600 mL of Solmix AP-1 was prepared in a beaker, and 20 mL of the obtained reaction liquid was slowly added dropwise while stirring with a stirrer. A white solid was precipitated in the solution. The precipitate was collected by suction filtration and then dried in a vacuum dryer set at 120° C. for 6 hours to obtain a target copolymer (1).

Example 2 Synthesis of Copolymer (2)/Synthesis of HXDI-DDM (1:1.5) Copolymer Under a nitrogen atmosphere, a 200 mL three-necked flask equipped with a reflux condenser, a temperature system and a dropping funnel. HXDI (1.97 g) and DMAc (47.5 g) were introduced into. It heated at 120 degreeC using the oil bath. Then, the solution in which DDM (3.02 g) was dissolved in DMAc (47.5 g) was introduced all at once by a syringe to start the reaction (HXDI-DDM=1:1.5). Then, while maintaining at 120° C., the mixture was stirred for 6 hours to obtain a transparent reaction liquid. The Mw and the PDI of the reaction solution determined by GPC analysis were 2,300 and 1.7, respectively.
Furthermore, 600 mL of Solmix AP-1 was prepared in a beaker, and 20 mL of the obtained reaction liquid was slowly added dropwise while stirring with a stirrer. A white solid was precipitated in the solution. The precipitate was collected by suction filtration, and then dried in a vacuum dryer set at 120°C for 6 hours to obtain a target copolymer (2).

Example 3 Synthesis of Copolymer (3)/Synthesis of HXDI-BAPP (1:1.2) Copolymer A 200 mL three-necked flask equipped with a reflux condenser, a temperature system and a dropping funnel under a nitrogen atmosphere. BAPP (14.3 g) and DMAc (57.4 g) were introduced into It heated at 120 degreeC using the oil bath. Then, a solution in which HXDI (5.66 g) was dissolved in DMAc (22.6 g) was introduced all at once by a syringe, and the reaction was initiated, HXDI-BAPP (1:1.2). Then, while maintaining at 120° C., the mixture was stirred for 6 hours to obtain a transparent reaction liquid. The Mw determined by GPC analysis of the reaction solution was 8,200 and the PDI was 2.7.
Furthermore, 600 mL of Solmix AP-1 was prepared in a beaker, and 20 mL of the obtained reaction liquid was slowly added dropwise while stirring with a stirrer. A white solid was precipitated in the solution. The precipitate was collected by suction filtration, and then dried in a vacuum dryer set at 120°C for 6 hours to obtain a target copolymer (3).

[Example 4] Synthesis of copolymer (4)/Synthesis of HXDI-BAPP (1:1.5) copolymer 100 mL three-necked flask equipped with a reflux condenser, a temperature system and a dropping funnel under a nitrogen atmosphere. BAPP (7.60 g) and DMAc (30.4 g) were introduced into. It heated at 120 degreeC using the oil bath. Then, a solution in which HXDI (2.40 g) was dissolved in DMAc (9.59 g) was collectively introduced with a syringe to start the reaction (HXDI-BAPP=1:1.5). Then, while maintaining at 120° C., the mixture was stirred for 6 hours to obtain a transparent reaction liquid. The Mw determined by GPC analysis of the reaction solution was 4,700, and the PDI was 1.5.
Furthermore, 600 mL of Solmix AP-1 was prepared in a beaker, and 20 mL of the obtained reaction liquid was slowly added dropwise while stirring with a stirrer. A white solid was precipitated in the solution. The precipitate was collected by suction filtration and dried in a vacuum dryer set at 120° C. for 6 hours to obtain the target copolymer (4).

Example 5 Synthesis of Copolymer (5)/Synthesis of HXDI-DGBE (1.5:1) Copolymer Under a nitrogen atmosphere, a 50 mL three-necked flask equipped with a reflux condenser, a temperature system and a dropping funnel. HXDI (0.55 g) and NMP (14.2 g) were introduced into. It heated at 120 degreeC using the oil bath. Then, a solution in which DGBE (0.95 g) was dissolved in NMP (14.2 g) was collectively introduced with a syringe to start the reaction (HXDI-DGBE=1.5:1). Then, while maintaining at 120° C., the mixture was stirred for 6 hours to obtain a transparent reaction liquid. The Mw determined by GPC analysis of the reaction solution was 1,300, and the PDI was 4.0.
Furthermore, the solvent was removed from the obtained reaction solution on a hot plate set to 120° C., and then the product was dried in a vacuum dryer set to 120° C. for 6 hours to obtain a target copolymer (5).

Example 6 Synthesis of Copolymer (6)/Synthesis of HXDI-FM3311 (1.5:1) Under a nitrogen atmosphere, a 100 mL three-necked flask equipped with a reflux condenser, a temperature system and a dropping funnel was equipped with HXDI( 2.37 g) and MIBK (32.0 g) were introduced. It heated at 120 degreeC using the oil bath. Then, a solution in which FM3311 (7.63 g) was dissolved in MIBK (8.0 g) was collectively introduced with a syringe to start the reaction (HXDI-FM3311=1.5:1). Then, while maintaining at 120° C., the mixture was stirred for 6 hours to obtain a transparent reaction liquid. The Mw determined by GPC analysis of the reaction solution was 9,700, and the PDI was 2.9.
Furthermore, the solvent was removed from the obtained reaction liquid on a hot plate set at 120° C., and then the product was dried in a vacuum dryer set at 120° C. for 6 hours to obtain a target copolymer (6).

[Comparative Example 1] Synthesis of copolymer (7)/synthesis of MDI-DDM (1:1.5) Under a nitrogen atmosphere, a 50 mL three-necked flask equipped with a reflux condenser, a temperature system and a dropping funnel was equipped with MDI( 0.68 g) and DMAc (14.2 g) were introduced. After stirring at room temperature, then, a solution in which DDM (0.82 g) was dissolved in DMAc (14.2 g) was collectively introduced with a syringe to start the reaction (MDI-DDM=1:1.5). .. After stirring for 1 hour at room temperature, the inside of the system became cloudy. Mw determined by GPC analysis of the precipitated copolymer was 8,000 and PDI was 2.0.
The precipitate was collected by suction filtration and then dried in a vacuum dryer set at 120° C. for 6 hours to obtain a target copolymer (7).

[Comparative Example 2] Synthesis of copolymer (8)/synthesis of MDI-DDM (1:1.2) Under a nitrogen atmosphere, a 50 mL three-necked flask equipped with a reflux condenser, a temperature system and a dropping funnel was used for MDI( 0.77 g) and DMAc (14.2 g) were introduced. After stirring at room temperature, then, a solution in which DDM (0.73 g) was dissolved in DMAc (14.2 g) was introduced all at once by a syringe to start the reaction (MDI-DDM=1:1.2). .. After stirring for 1 hour at room temperature, the inside of the system became cloudy. The Mw of the precipitated copolymer determined by GPC analysis was 15,000, and the PDI was 2.2.
The precipitate was collected by suction filtration, and then dried in a vacuum dryer set at 120°C for 6 hours to obtain a target copolymer (8).

[Comparative Example 3] Synthesis of copolymer (9)/Synthesis of HDI-DDM (1:1.5) Under a nitrogen atmosphere, a 50 mL three-necked flask equipped with a reflux condenser, a temperature system and a dropping funnel was charged with HDI( 0.69 g) and DMAc (14.2 g) were introduced. After stirring at room temperature, a solution in which DDM (0.81 g) was dissolved in DMAc (14.2 g) was then introduced all at once with a syringe to start the reaction (HDI-DDM=1:1.5). .. Immediately after starting the reaction, the inside of the system became cloudy. The precipitated copolymer was insoluble in a general organic solvent and could not be measured by GPC.
The precipitate was collected by suction filtration, and then dried in a vacuum dryer set at 120°C for 6 hours to obtain a target copolymer (9).

Comparative Example 4 Synthesis of Copolymer (10)/Synthesis of MDI-HXDA (1:1.2) Under a nitrogen atmosphere, a 50 mL three-necked flask equipped with a reflux condenser, a temperature system and a dropping funnel was equipped with MDI( 0.89 g) and DMAc (14.2 g) were introduced. After stirring at room temperature, then, a solution prepared by dissolving HXDA (0.75 g) in DMAc (17.1 g) was introduced all at once by a syringe to start the reaction (MDI-HXDA=1:1.2). .. Immediately after starting the reaction, the inside of the system became cloudy. The precipitated copolymer was insoluble in a general organic solvent and could not be measured by GPC.

[Evaluation of transparency of cured film on glass plate]
The obtained copolymers (1) to (4) were redissolved in a DMAc solvent to a solid content concentration of 40 wt% to obtain coating solutions (1) to (4). Further, the copolymer (5) was redissolved in an NMP solvent and the copolymer (6) in a MIBK solvent to a solid content concentration of 40 wt %, to obtain coating solutions (5) and (6), respectively. .. The obtained coating liquid was applied on a glass plate (Eagle XG Corning Co., Ltd., 0.7 mm thick) using a spin coater (Opticoat MS-A150, Mikasa Co., Ltd.) under the conditions of 300 rpm and 10 seconds. Spin coating was performed to form a wet film. It was heat-treated for 10 minutes on a hot plate (HI-200A, manufactured by AS ONE Co., Ltd.) set at 150° C. to obtain cured films (1) to (6) having a film thickness of about 50 μm.

Table 1 shows the polymerization conditions of Examples 1 to 6 and Comparative Examples 1 to 4 and the molecular weight of the copolymer.

Table 2 shows the results of measuring Td ₅ and Tmg of the copolymers (1) to (9).

Table 3 shows the results of measuring the total light transmittance and haze of the cured films (1) to (6).

As is clear from the results in Table 1, the copolymers of Examples 1 to 6 have excellent solubility in organic solvents. Furthermore, as is clear from the results in Table 2, the obtained copolymer also has excellent heat resistance. Also, the glass transition temperature can be adjusted by changing the composition of the copolymer. Further, as is clear from the results in Table 3, when the obtained copolymer is used as a film, it has excellent transparency.

From the above, the copolymer of the present invention is soluble in a general-purpose organic solvent, excellent in heat resistance and transparency, since it has an amine or urea in the molecule, by introducing various functional groups, It is also useful as a reactive intermediate that can be converted into a reactive oligomer.

[Production Example 1] Synthesis of copolymer (11)
Under 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 the mixture was dissolved using a stirrer. It heated at 120 degreeC using the oil bath. Then, a solution of HXDI (1.94 g) dissolved in DEF (5.3 ml), which had been adjusted to a 30 ml sample bottle in advance, 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, the reaction was carried out for 4 hours while maintaining the temperature at 120° C., followed by cooling with a water bath and adding 1 ml of methanol to quench excess isocyanate groups. Copolymer (11), which is a polyurea alternating copolymer containing the structural unit of the intended alternating copolymer, having an Mw of 126,000 and a PDI of 20.0 determined by GPC analysis of the reaction solution was obtained. ..

[Production Example 2] Synthesis of copolymer (12)
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, a thermometer and a dropping funnel. While maintaining the cooled state by immersing the flask in a water bath, Silaplane FM3311 (12.3 g) was added dropwise using a dropping funnel over 5 minutes (HXDI:FM3311=1.06:1, molar ratio). Further, FM3311 attached to the dropping funnel was washed off with DMAc (10.0 g) and introduced into the flask. Then, the reaction was continued for 2 hours to obtain a transparent reaction liquid.
The Mw determined by GPC analysis of the reaction solution was 34,000 and the PDI was 7.0, and a copolymer (12), which was a polyurea-based alternating copolymer containing the structural unit of the desired alternating copolymer, was obtained. It was

Table 4 shows the compositions, Mw, and PDI of the obtained copolymers (11) to (12).

[Example 11] Production of resin film (11) A release film (product name: NSD-100, 100 m, manufactured by Fujimori Industry Co., Ltd.) was used as a substrate. The copolymer (11) (concentration: 19%, solvent: DEF) synthesized in Production Example 1 was cast on a base material, and a Baker type film applicator (Product name: No. 510 Baker type film applicator, Yasuda Seiki Co., Ltd.) was used. A coating film having a uniform film thickness was prepared by adjusting the scales on both sides of the product) to adjust the distance between the applicator and the substrate. After drying at 120° C. for 15 minutes, the release film was removed to obtain a single-layer resin film (11) having a film thickness of 40 μm.

[Example 12] Production of resin film (12)
A single-layer resin film (12) was obtained in the same manner as in Example 11 except that the copolymer (12) was used instead of the copolymer (11) and the scale, concentration and solvent of the applicator were changed. It was

Table 5 shows the characteristics and film thickness of the obtained single-layer resin film.

[Comparative Example 11]
The transparent polyimide (film 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.

<Shock absorption test>
A chrome steel ball (model number: CR-3/4, material: chrome steel (SUJ-2), size: 3/4 inch, manufactured by AS ONE Corp.) was dropped from a height of 10 cm. The resin film sample was placed at the drop point, and SUS430 (thickness 0.5 cm) was placed below it. A general-purpose piezoelectric load cell (model: 208C05, manufactured by PCB Piezotronics) is installed under SUS430, and an oscilloscope (model number: DS-5107B, manufactured by Iwasaki Tsushinki Co., Ltd.) is used to measure the impact force applied to the resin film sample when dropped. Measured. 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 x 75 mm, thickness: 1 mm, manufactured by As One Co., Ltd.) was cut into lengths of 25 mm x 30 mm, and a resin film was placed on or under the glass. Were prepared, respectively.

<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 a part of the impact force contributed to the glass breakage, and therefore it was impossible to measure in the impact absorption test.

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

Test results:
From Tables 6 and 7, the glass is broken by the falling ball only with the glass, but the glass is protected not only when the resin films of Examples 11 to 12 are placed on the glass but also when the film is placed below the glass. It became clear that there is a function to do.
Further, the transparent polyimide protects the glass more than the resin films of Examples 11 to 12 because the glass breaks when the film is placed on the glass, but the glass does not break when the film is placed below. It turns out that the function is small.

All publications, including publications, patent applications and patents, cited in this specification are specifically incorporated by reference and incorporated by reference in their entirety, and all of their contents set forth herein. To the same extent, they are incorporated by reference.

The use of nouns and similar reference terms used in connection with the description of the invention (particularly in connection with the claims below) is not expressly indicated herein or otherwise contradicted by context. , Singular and plural. The terms "comprising," "having," "including," and "including" are to be construed as open-ended terms (ie, meaning "including but not limited to"), unless otherwise specified. The appearance of numerical ranges in this specification is merely intended to serve as a shorthand notation for individually referring to each value falling within the range, unless stated otherwise herein. 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 clearly contradicted by context. As used herein, any example or exemplary phraseology (eg, “such as”) is intended only to better describe the invention and, unless otherwise claimed, provides a limitation on the scope of the invention. is not. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of these preferred embodiments will be apparent to those of skill in the art upon reading the above description. The inventor anticipates that skilled persons will apply such modifications as appropriate, and plans that the present invention may be carried out in other ways than those 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, unless otherwise indicated herein or clearly contradicted by context, any combination of the above elements in all variations is encompassed by the invention.

Claims (15)

A polyaddition alternating copolymer of a diisocyanate compound <A> and a diamine compound <B>, which contains a repeating unit represented by the following formula (1) and has a weight average molecular weight of 500 to 300,000.
Alternating polyurea copolymer.

-[(A)-(B)]- Formula (1)
(In the formula, (A) represents at least one kind of an aliphatic diisocyanate structural unit having a cyclic structure in the molecule,
(B) is at least one selected independently from the structural units of aliphatic diamine, aromatic diamine, diamine having an ether bond, and diamine having a siloxane skeleton. ) The diisocyanate compound <A> is a compound represented by the following formulas (I) to (X),
In the following formulas (I) to (X), R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or alkyl having 1 to 7 carbon atoms,
X is independently alkylene having 1 to 7 carbon atoms,
Y are each independently oxygen, sulfur, a straight chain or branched alkylene having a carbon number of _{1~7, -C (CF 3) 2} - or -SO ₂ - is,
The polyurea-based alternating copolymer according to claim 1.

The diamine compound <B> is at least one selected from linear aliphatic diamines, aliphatic diamines having an ether bond, and diamines having a siloxane skeleton.
The polyurea-based alternating copolymer according to claim 1 or 2. The diamine compound <B> is at least one selected from aromatic diamine, aromatic diamine having an ether bond, and aliphatic diamine having a cyclic skeleton,
The polyurea-based alternating copolymer according to claim 1 or 2. Terminal is any one of a good -NH ₂ or -NCO also be end-capped,
The polyurea-based alternating copolymer according to any one of claims 1 to 4. 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 adjusted to satisfy the relationship of 1.06≦n2/n1≦1.9. Thereby, both ends are -NH ₂ which may be end-capped,
The polyurea alternating copolymer according to any one of claims 1 to 5. 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 adjusted to satisfy the relationship of 1.06≦n1/n2≦1.9. Thereby, both ends are -NCO which may be end-capped.
The polyurea alternating copolymer according to any one of claims 1 to 5. An alternating copolymer of polyurea according to any one of claims 1 to 7;
A solvent that dissolves the polyurea alternating copolymer;
Resin composition. The solvent is propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, 4-methyl. 2-pentanone, N,N-dimethylpropionamide, tetramethylurea, at least one of dimethylsulfoxide,
The resin composition according to claim 8. A solid content obtained by removing the solvent from the resin composition according to claim 8 or 9,
Paint film. Formed from a solid content obtained by removing the solvent from the resin composition according to claim 8 or 9,
Resin film. At least two layers of a resin film formed from a solid content obtained by removing the solvent from the resin composition according to claim 8 or 9,
Resin film. The resin film according to claim 11 or 12,
OLED element. The OLED element according to claim 13;
Light emitting device. The diisocyanate compound <A> and the diamine compound <B> according to any one of claims 1 to 7 are dissolved in one or more organic solvents, and a copolymer is obtained by solution polymerization. Characterized by,
A method for producing a polyurea alternating copolymer.

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