JP2020152833A - Side chain silicone type polyurethane and block copolymer - Google Patents

Abstract

To provide a side chain silicone type polyurethane that has excellent characteristics in transparency, extensibility, flexibility and heat resistance, and can introduce various functional groups by a solution reaction in a conventional organic solvent, a novel block copolymer having side chain silicone type polyurethane, and its manufacturing method.SOLUTION: An alternating copolymer that is an addition polymer of a diisocyanate compound <A>, and a diol compound <CSi> represented by the following formula (1), contains a repeating unit represented by the following formula (2) and has a weight average molecular weight of 500 to 300,000. (In the formula (1), n is an integer of 0 to 300, R1 to R8 each is hydrogen or alkyl having 1 to 30 carbons, X1 to X4 each is straight chain alkylene having 1 to 20 carbons.) -[(A)-(CSi)-]- formula (2) (In the formula (2), (A) and (CSi) are structural units corresponding to a diisocyanate compound <A> and a diol compound (CSi).)SELECTED DRAWING: None

Description

The present invention relates to a side chain silicone type polyurethane and block copolymer useful as a highly elastic recovery material, and a method for producing the same, assuming use in a flexible device in the field of electronic information materials. Furthermore, it relates to materials that can be horizontally deployed in 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 become widespread, and smartphones, mobile terminals such as PNDs (personal navigation devices), and wearable displays such as Google Glass have become popular. Take as an example.

Further, with the practical use of organic EL displays, further weight reduction is required, and a method of switching a part of a member from glass or thin film glass to plastic is adopted. However, while thin film glass has excellent heat resistance, it is extremely fragile, and plastics (particularly PET, PC, PMMA, cycloolefin, etc.) have the characteristics of being lightweight and highly transparent, but have impact resistance and scratch resistance. Due to the lack of mechanical properties such as, the development of new functional plastics has been required.

Patent Document 1 discloses a coating agent for a glass substrate having excellent scratch resistance and excellent adhesion to glass and anti-scattering property (paragraph 0019). However, although the obtained glass coating layer has excellent scratch resistance and shatterproof properties, it is insufficient when used in recent smartphones and wearable displays.

On the other hand, Patent Document 2 describes a new product having high hardness and toughness useful as various rolls such as calendar rolls used for papermaking, woven fabrics, magnetic tapes, casters and other general molding resins, and excellent heat resistance. Polyurea resin is disclosed (paragraph 0001). However, the technique relates to a general molding resin used by injecting it into a mold, and is not intended to be applied to a film-shaped mobile terminal or the like in terms of handling and the like.

Further, Patent Document 3 states that it can be obtained by heat treatment at a low temperature, has good adhesion to a substrate and a sealing material, has improved tin plating resistance, and further has a warp. Is unlikely to occur, has excellent heat resistance, solder flux resistance, solvent resistance, chemical resistance, bending resistance, and electrical characteristics, and can be applied well on substrates such as flexible wiring boards. A polyimide siloxane-based insulating film composition for forming an insulating film of a component or the like is disclosed. However, this technology is intended to be applied to flexible wiring boards, and no consideration has been given to the transparency required for display applications.

Japanese Unexamined Patent Publication No. 2006-290696 Japanese Unexamined Patent Publication No. 5-194695 Japanese Unexamined Patent Publication No. 2004-231757

An object of the present invention is that it has excellent properties of transparency, extensibility, flexibility, and heat resistance, and is soluble in a general-purpose organic solvent. Therefore, various functional groups can be introduced by a solution reaction. It is an object of the present invention to provide a side chain silicone type polyurethane and a novel block copolymer having a side chain silicone type polyurethane, which are also useful as possible reactive intermediates, and a method for producing the same.

Furthermore, since the novel block copolymer of the present invention has a hydroxyl group or an isocyanate at the molecular terminal and has a urea structure and a urethane structure in the molecule, it has, for example, a (meth) acrylate having an isocyanate group or an epoxy group ( It can react with a meta) acrylate, and a vinyl-based functional group can be easily introduced.

As a result of diligent research to achieve the above object, the present inventor has completed the present invention of the aspects described in the following [1] to [18].

[1] An addition copolymer of a diisocyanate compound <A> and a diol compound < ^CS > represented by the following formula (1), which comprises a repeating unit represented by the following formula (2) and has a weight average molecular weight. A polyurethane-based alternating copolymer having a molecular weight of 500,000 to 300,000.

(In equation (1)
n is an integer from 0 to 300
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen or alkyl with 1 to 30 carbon atoms, X ₁ , X ₂ , X ₃ and Each of X ₄ is a linear alkylene having 1 to 20 carbon atoms or a branched alkylene having 3 to 20 carbon atoms. )

-[(A)-(C ^Si )-]-Equation (2)
(A) and (C ^Si ) in the formula (2) are structural units corresponding to the diisocyanate compound <A> and the diol compound <C ^Si >.

Examples of aspects of the present invention are shown below.

[2] The polyurethane-based alternating copolymer according to [1], wherein the diol compound < ^CS > is a diol compound represented by the formula (1-1).

(In equation (1-1)
n is an integer from 0 to 300
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen or alkyl having 1 to 30 carbon atoms. )

[3] The polyurethane alternating copolymer according to [1], wherein the diol compound < ^CS > is a diol compound represented by the formula (1-2).

(In equation (1-2)
n is an integer from 0 to 300
R ₉ and R ₁₀ are independently alkyl having 1 to 4 carbon atoms. )

[4] The polyurethane alternating according to any one of [1] to [3], wherein the diisocyanate compound <A> is at least one kind of aliphatic diisocyanate having a cyclic structure in the molecule. Copolymer.

[5] The polyurethane alternating copolymer according to any one of [1] to [4], wherein the diisocyanate compound <A> is a compound represented by the following formulas (I) to (X).

(In formulas (I) to (X), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are independently hydrogen or alkyl having 1 to 7 carbon atoms.
X is an alkylene having 1 to 7 carbon atoms independently of each other.
Y is independently oxygen, sulfur, a linear or branched alkylene having 1 to 7 carbon atoms, -C (CF ₃ ) _2- or -SO _2- . )

[6] The polyurethane alternating copolymer according to any one of [1] to [5], which is either -OH or -NCO whose end may be end-sealed.

[7] With the polyurethane alternating copolymer according to any one of [1] to [6];
A resin composition containing a solvent that dissolves the polyurethane alternating copolymer;

[8] The solvent used is propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, The resin composition according to [7], which comprises at least one of 4-methyl-2-pentanone, N, N-dimethylpropionamide, tetramethylurea, and dimethyl sulfoxide.

[9] The diisocyanate compound <A> and the diol compound < ^CS > represented by the following formula (1) are dissolved in one or more kinds of organic solvents, and a copolymer is obtained by solution polymerization. A method for producing a polyurethane alternating copolymer (containing a repeating unit represented by the following formula (2) and having a weight average molecular weight of 500,000 to 300,000).

(In equation (1)
n is an integer from 0 to 300
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen or alkyl with 1 to 30 carbon atoms, X ₁ , X ₂ , X ₃ and Each of X ₄ is a linear or branched alkylene having 1 to 20 carbon atoms. )
-[(A)-(C ^Si )-]-Equation (2)
(A) and (C ^Si ) in the formula (1) are structural units corresponding to the diisocyanate compound <A> and the diol compound <C ^Si >.

[10] It contains a structural unit which is a double-addition copolymer of the alternate copolymer 1 and the alternate copolymer 2 represented by the following formula (3), and has a weight average molecular weight of 5,000 to 300,000. , A block copolymer having both ends -NH ₂ or -NCO.

-[(Alternative copolymer 1)-(Alternative copolymer 2)]-Formula (3)
Alternate copolymer 1: Polyurethane alternating copolymer according to any one of [1] to [6] Alternating copolymer 2: Double addition copolymer of diisocyanate compound <A'> and diamine compound <B> A polyurea-based alternating copolymer represented by the following formula (4), which is a coalescence-[(A')-(B)]-formula (4)
(A') is an aliphatic isocyanate structural unit having an intramolecular cyclic structure independently of each other;
(B) is a structural unit independently selected from an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton;
However, when both ends of the alternating copolymer 1 are -NCO, both ends of the alternating copolymer 2 are -OH;
When both ends of the alternating copolymer 1 are -NH ₂ , both ends of the alternating copolymer 2 are -NCO.

[11] The block copolymer according to [10], wherein both ends of the alternate copolymer 1 are −OH and both ends of the alternate copolymer 2 are −NCO.

[12] The block copolymer according to [10], wherein both ends of the alternate copolymer 1 are -NCO and both ends of the alternate copolymer 2 are -NH ₂ .

[13] The diisocyanate compound <A'> is a compound represented by the following formulas (I) to (X).
In the following formulas (I) to (X), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are independently hydrogen or alkyl having 1 to 7 carbon atoms.
X is an alkylene having 1 to 7 carbon atoms independently of each other.
Y is independently oxygen, sulfur, a linear or branched alkylene with 1 to 7 carbon atoms, -C (CF ₃ ) _2- or -SO _2- .
The block copolymer according to any one of [10] to [12].

[14] The block copolymer according to any one of [10] to [13], which is −OH, −NH ₂ or −NCO whose ends may be end-sealed.

[15] With the block copolymer according to any one of [10] to [14];
A resin composition containing a solvent that dissolves the block copolymer.

[16] The solvent used 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 [15], which comprises at least one of 4-methyl-2-pentanone, N, N-dimethylpropionamide, tetramethylurea, and dimethyl sulfoxide.

[17] A coating film containing a solid content obtained by removing a solvent from the resin composition according to [15] or [16].

[18] A resin film formed from a solid content obtained by removing a solvent from the resin composition according to [15] or [16].

1 Polyurethane-based alternating copolymer The polyurethane-based alternating copolymer of the present invention is an addition polymer of a diisocyanate compound <A> and a diol compound < ^CS > represented by the following formula (1), and has the following formula. It contains the repeating unit represented by (2) and has a weight average molecular weight of 5 to 300,000.

(In equation (1)
n is an integer from 0 to 300
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are independent hydrogens or alkyls with 1 to 30 carbon atoms, X ₁ , X ₂ , X ₃ , Each of X ₄ independently represents a linear or branched alkylene having 1 to 20 carbon atoms. )

-[(A)-(C ^Si )-]-Equation (2)
(A) and (C ^Si ) in the formula (2) are structural units corresponding to the diisocyanate compound <A> and the diol compound <C ^Si >.

The polyurethane-based alternating copolymer is obtained by double-adding the diisocyanate compound <A> and the diol compound < ^CS >. The diisocyanate compound <A> and the diol compound < ^CS > correspond to the structural unit (A) and the structural unit ( ^CS ) in the alternating copolymer, respectively. The binding sites between the structural units (A) and ( ^CS ) are all urethane structures (-NH-CO-O-).

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 a compound having two isocyanate groups in the molecule. An example thereof is an aliphatic diisocyanate compound. The "aliphatic diisocyanate compound" referred to in the present invention has two isocyanate groups in the molecule, in which an isocyanate group is directly bonded to a linear or branched aliphatic hydrocarbon or an aliphatic ring carbon. It is a compound that has. When an aliphatic diisocyanate compound is used in the present invention, it is preferably an aliphatic diisocyanate compound having a cyclic structure in the molecule in terms of reactivity and solubility in a solvent. Specific examples thereof include diisocyanate compounds represented by the following formulas (I) to (X).

In the following formulas (I) to (X), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are independently hydrogen or alkyl having 1 to 7 carbon atoms.
X is an alkylene having 1 to 7 carbon atoms independently of each other.
Y is independently oxygen, sulfur, a linear or branched alkylene having 1 to 7 carbon atoms, -C (CF ₃ ) _2- or -SO _2- .

Among the above specific examples, the diisocyanate compound represented by the formula (V), (VI) or (VIII) is preferable because of its high solubility in a solvent. Further, when high transparency and heat resistance are required, the diisocyanate compound represented by the formula (V) or (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 a compound having two isocyanate groups in the molecule, but is disclosed in, for example, JP-A-2016-199694. Examples of the compound.

Specific examples of aliphatic diisocyanates having a cyclic structure in the molecule; isophorone diisocyanate, (bicyclo [2.2.1] heptane-2,5-diyl) bismethylene diisocyanate, (bicyclo [2.2.1] heptane- 2,6-diyl) bismethylene diisocyanate, 2β, 5α-bis (isocyanate) norbornan, 2β, 5β-bis (isocyanate) norbornan, 2β, 6α-bis (isocyanate) norbornan, 2β, 6β-bis (isocyanate) norbornan, 2,6-di (isocyanate methyl) furan, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, dicyclohexylmethane diisocyanate, 4,4-isopropyridenebis (cyclohexylisocyanate), cyclohexane Diisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethylmethanediisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanate-n-butylidene) pentaerythritol, diisocyanate dimerate, 3,8-bis (isocyanate methyl) Tricyclodecane, 3,9-bis (isocyanatemethyl) tricyclodecane, 4,8-bis (isocyanatemethyl) tricyclodecane, 4,9-bis (isocyanatemethyl) tricyclodecane, 1,5-diisocyanatedecalin, Included are 2,7-diisocyanate decarinate, 1,4-diisocyanate decalinate, 2,6-diisocyanate decalinate, dicyclohexylsulfide-4,4'-diisocyanate, and tricyclothiaoctanediisocyanate.

As the diisocyanate compound described above, only one type may be used, or two or more types may be mixed and used.

1.2 Diol compound < ^CS >
The diol compound < ^CS > used in the polyurethane-based alternating copolymer of the present invention is a diol compound represented by the following formula (1). The diol compound < ^CS > is a compound containing a silicone chain (siloxane bond serving as a main chain), one end of which is modified to two hydroxyl groups.

In equation (1), n is an integer from 0 to 300.

It is preferable to set n of the silicone chain to 0 to 300 because the flexibility, low wear resistance, and water repellency of the obtained polyurethane alternating copolymer can be adjusted.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are independently hydrogen or alkyl having 1 to 30 carbon atoms.
X ₁ , X ₂ , X ₃ , and X ₄ are independently linear or branched alkylenes having 1 to 20 carbon atoms. By adjusting these lengths, it is possible to adjust the leveling property to the base material and the compatibility with the composition, which is preferable.

With this configuration, highly reactive hydroxyl groups react and the silicones associate in a comb-shaped manner to form a cured film that is endowed with the properties of silicones: flexibility, low abrasion resistance, and water repellency. Can be made.

As a specific embodiment of the diol compound < ^CS >, a diol compound represented by the formula (1-1) can be mentioned.

In equation (1-1), n is an integer from 0 to 300.
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are independently hydrogen or alkyl having 1 to 30 carbon atoms.

As a further specific example of the diol compound < ^CS >, the diol compound represented by the formula (1-2) can be mentioned.

In equation (1-2), n is an integer from 0 to 300. R ₉ and R ₁₀ are alkyl having 1 to 4 carbon atoms. By adjusting these lengths, the leveling property to the base material and the compatibility with the composition can be further adjusted, which is preferable.

With such a configuration, the raw material can be easily obtained. In addition, by reacting highly reactive hydroxyl groups and associating the silicone in a comb-shaped hanging state, a polyurethane-based alternating copolymer imparted with the properties of silicone such as flexibility, low abrasion resistance, and water repellency can be obtained. Can be made.

Diol compound further embodiment of ^{<C Si>,} as Silaplane FM-DA series manufactured JNC (Ltd.), SILAPLANE FM-DA11 (average molecular weight Mn; 1,000), SILAPLANE FM-DA21 (average molecular weight Mn 5,000), hydroxyl group-containing siloxane compounds such as silaplane FM-DA26 (average molecular weight Mn; 15,000) can be mentioned. Among these, silaplane FM-DA11 is preferable from the viewpoint of solubility.

Regarding the method for producing a hydroxyl group-containing siloxane compound, Japanese Patent No. 3661807 can be referred to.

1.3 Weight Average Molecular Weight In the present invention, a polyurethane-based alternating copolymer having a weight average molecular weight of 500,000 to 300,000 can be preferably used. Polyurethane-based alternating copolymers having a weight average molecular weight of 500 or more have good heat resistance and mechanical properties, and polyurethane-based alternating copolymers having a weight average molecular weight of 300,000 or less are soluble in general-purpose organic solvents. Therefore, it is useful as a reactive intermediate that has good handleability and can introduce various functional groups in a solution reaction. Further, in the present invention, in order to further improve the solubility and handleability of the polyurethane-based alternating copolymer in a solvent, the weight average molecular weight thereof is preferably 500 to 100,000, preferably 500 to 50,000. Is even more preferable.

The weight average molecular weight of the polyurethane-based alternating copolymer can be measured by gel permeation chromatography (GPC). Specifically, the concentration of the reactive polyurea in a solution prepared by dissolving 10 mm mol / L of lithium bromide in a solvent obtained by mixing tetrahydrofuran (THF) and N, N-dimethylformamide (DMF) in the obtained reactive polyurea. Is diluted to about 1% by weight, measured by gel permeation chromatography (GPC) under the conditions shown below, and converted to polystyrene.
<GPC>
Equipment: LC-2000Plus series manufactured by JASCO Corporation (Detector: Differential refractometer)
Solvent: THF / DMF = 1/1 (v / v), lithium bromide 10 mm mol / L content flow velocity: 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

1.4 Terminals The polyurethane-based alternating copolymer of the present invention may have either -OH or -NCO at the end, but the polyurethane-based alternating copolymer having both ends of -OH, or both ends of- A polyurethane-based alternating copolymer which is NCO can be particularly preferably used. Such a polyurea-based alternating copolymer is chemically stable and can be preferably used because it leads to control of the reactive group to −OH or −NCO, particularly when used as a reactive intermediate.

In the polyurethane-based alternating copolymer having −OH at both ends, for example, when the number of moles of the diisocyanate compound <A> is n1 and the number of moles of the diol compound < ^CS > is n2, the number of moles thereof is 1. It can be obtained by adjusting so that the relationship is .05 ≦ n2 / n1 ≦ 1.95, but more preferably 1.1 ≦ n2 / n1 ≦ 1.8, and further preferably 1.1 ≦ n2 /. n1 ≦ 1.6.

By increasing the number of moles of the diol compound < ^CS >, a polyurethane-based alternating copolymer having both ends of −OH, which is chemically stable and has a weight average molecular weight in a preferable range, can be obtained.

In the polyurethane-based alternating copolymer having −NCO at both ends, for example, when the number of moles of the diisocyanate compound <A> is n1 and the number of moles of the diol compound < ^CS > is n2, the number of moles of each is 1. It can be obtained by adjusting so that the relationship is .05 ≦ n1 / n2 ≦ 1.95, but more preferably 1.1 ≦ n1 / n2 ≦ 1.8, and further preferably 1.1 ≦ n1 /. n2 ≦ 1.6.

By making the number of moles of the diisocyanate compound <A> excessive, it is possible to obtain a polyurethane-based alternating copolymer having -NCO at both ends, which is chemically stable and has a weight average molecular weight in a preferable range.

1.5 End-sealing When the terminal-reactive group of the polyurethane-based alternating copolymer is not used, the terminal-reactive group -OH or -NCO can be sealed before use.

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

Specific examples of compounds having -NH ₂ groups that can be used as an end-capping agent include 1-aminobutane, 4-ethynylaniline, 3-ethynylaniline, propargylamine, 3-aminobutin, 4-aminobutin, and 5-aminopentin. , 4-Aminopentin, allylamine, 7-aminoheptin, m-aminostyrene, p-aminostyrene, m-amino-α-methylstyrene, 3-aminophenylacetylene, 4-aminophenylacetylene. Among these, 1-aminobutane is preferable from the viewpoint of excellent reactivity. Only one of these monoamine compounds may be used, or two or more of these monoamine compounds may be mixed and used.

Specific examples of compounds having a -NH group that can be used as an end-capping agent include dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylethylamine, N-methylpropylamine, N-methylbutylamine, and N. -Ethylpropylamine, N-ethylbutylamine, morpholine can be mentioned. Only one of these monoamine compounds may be used, or two or more of these monoamine compounds may be mixed and used.

Specific examples of the compound having a −OH group that can be used as an end-capping agent include a monoalcohol compound having 1 to 18 carbon atoms. Examples of monoalcohol compounds having 1 to 18 carbon atoms include linear monools (methanol, ethanol, n-propanol, n-butanol, pentanol, hexanol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, and tri). Decyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, etc.); Monools with branched chains (isopropanol, sec-, iso- or tert-butanol, neopentyl alcohol, 3-methyl-pentanol and 2-ethylhexanol) Etc.); Monools having a cyclic group having 6 to 10 carbon atoms [monool containing an alicyclic group (cyclohexanol, etc.), monool containing an aromatic ring (benzyl alcohol, etc.), etc.] can be mentioned. Further, specific examples of the compound having a -OH group include polymer monools (polyester monool, polyether monool, polyether ester monool, etc.), cellosolves and carbitols. Of these, linear monool is preferred. Specifically, methanol, ethanol, n-propanol, n-butanol and the like.

Only one of these monoalcohol compounds may be used, or two or more of these monoalcohol compounds may be mixed and used.

When the terminal reactive group is -OH, a compound having a -NCO group can be used as the terminal encapsulant.

Specific examples of the compound having a -NCO group that can be used as the terminal sealant include phenyl isocyanate, toluylene isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate. Only one of these monoisocyanate compounds may be used, or two or more of these monoisocyanate compounds may be mixed and used.

2 Method for Producing Polyurethane-based Alternate Copolymer In the method for producing the reactive polyurea of the present invention, the diisocyanate compound <A> and the diol compound < ^CS > are dissolved in one or more organic solvents and solution-polymerized. It is characterized in that a copolymer is obtained by.

<A> said diisocyanate compound, the Jijioru compound dissolved <C ^Si>, a reaction solvent used for obtaining the copolymer by solution polymerization, intended to polyurethane alternating copolymer is limited in particular as long synthesis Absent. Examples of the reaction solvent include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and methyl 3-methoxypropionate. Ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, Diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl Ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether (1-methoxy- 2-Propanol), triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl -2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethyl Formamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethi Lu-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 Examples thereof include propyl alcohol, N, N-dimethylpropionamide, tetramethylurea, and dimethyl sulfoxide.

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 dimethyl sulfoxide because the polyurethane-based alternating copolymer has good solubility and uniform polymerization proceeds.

Only one kind of these reaction solvents may be used, or two or more kinds may be mixed and used. Further, other solvents may be mixed and used in addition to the above reaction solvent.

It is preferable to use 50 parts by weight or more of the reaction solvent with respect to 100 parts by weight in total of the diisocyanate compound <A> and the diol compound < ^CS > because the reaction proceeds smoothly. The reaction is preferably carried out at 0 to 150 ° C. for 0.2 to 3 hours.

Further, the order of adding the reaction raw materials to the reaction system is not particularly limited. That is, a method of simultaneously adding the diisocyanate compound <A> and the diol compound <C ^Si > to the reaction solvent, a method of dissolving the diol compound <C ^Si > in the reaction solvent, and then adding the diisocyanate compound <A>, the diisocyanate compound. Any method can be used, such as a method in which <A> is dissolved in a reaction solvent and then a diol compound < ^CS > is added.

4 Resin Composition The resin composition of the present invention is a composition containing the polyurethane-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 polyurethane-based alternating copolymer. For example, the reaction solvent used in the production of the polyurethane-based alternating copolymer can be used as it is, or another solvent can be added and used as a mixed solvent.

Further, the polyurethane-based alternating copolymer can be isolated as a solid component and then redissolved in a desired solvent for use. As a method for isolating the reactive polyurea, a solution containing the reactive polyurea and the reaction solvent is poured into a poor solvent for the polyurethane-based alternating copolymer such as methanol, ethanol, and isopropyl ether to make the polyurethane-based alternating copolymer. Can be mentioned as a method of precipitating and separating by filtration, washing, drying or the like. By performing such an operation, it is possible to remove the catalyst used in the production of the polyurethane-based alternating copolymer.

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, dimethyl sulfoxide can be mentioned. Only one of these solvents may be used, or two or more of these solvents may be mixed and used.

The concentration of the polyurethane-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 for 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, and is preferably adjusted to the range of 10 to 50,000 mPa · s.

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

The block copolymer of the present invention contains a structural unit which is a heavy addition copolymer of the alternate copolymer 1 and the alternate copolymer 2 represented by the following formula (3), and has a weight average molecular weight of 5, It is a block copolymer of 000 to 300,000 with both ends being -NH ₂ or -NCO.

-[(Alternative copolymer 1)-(Alternative copolymer 2)]-Formula (3)
However, when both ends of the alternating copolymer 1 are -NCO, both ends of the alternating copolymer 2 are -NH ₂ ;
When both ends of the alternating copolymer 1 are −OH, both ends of the alternating copolymer 2 are −NCO.

The elements constituting this block copolymer will be described in order below.

1 Alternating copolymer 1
The alternating copolymer 1 is the same as the polyurethane-based alternating copolymer of the present invention.

That is, the alternating copolymer 1 is an addition polymer of the diisocyanate compound <A> and the diol compound < ^CS > represented by the following formula (1), and is a repeating unit represented by the following formula (2). It is a polyurethane-based alternating copolymer containing the above and having a weight average molecular weight of 500,000 to 300,000.

(In equation (1)
n is an integer from 0 to 300
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen or alkyl having 1 to 30 carbon atoms, X ₁ , X ₂ , X ₃ , X ₄ each independently represents an organic silicon compound is a linear or branched alkylene having 1 to 20 carbon atoms. )

-[(A)-(C ^Si )-]-Equation (2)
(A) and (C ^Si ) in the formula (2) are structural units corresponding to the diisocyanate compound <A> and the diol compound <C ^Si >.

The diisocyanate compound <A> is also as described in the description of the polyurethane alternating copolymer of the present invention.

The alternating copolymer 1 is obtained by double-adding the diisocyanate compound <A> and the diol compound < ^CS >. The diisocyanate compound <A> and the diol compound < ^CS > correspond to the structural unit (A) and the structural unit ( ^CS ) in the alternating copolymer 1. The binding site between the structural units (A) and ( ^CS ) is a urethane structure (-NH-CO-O-).

The structural unit of the alternate copolymer 1 is considered to be a structural unit (soft segment) that contributes to solubility, flexibility, extensibility, flexibility, low abrasion resistance, and water repellency in the physical properties of the block copolymer. Be done.

2 Alternating copolymer 2
The alternating copolymer 2 is obtained by double-adding 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 2, respectively. The binding site between the structural units (A') and (B) is a urea structure (-NH-CO-NH-).

The structural unit of the alternate copolymer 2 is considered to be a structural unit (hard segment) that contributes to rigidity and heat resistance in the physical properties of the block copolymer.

2.1 Diisocyanate compound <A'>
The diisocyanate compound <A'> that can be used in the present invention may be the same as or different from the diisocyanate compound <A> used in the alternating copolymer 1, and is an aliphatic diisocyanate having a cyclic structure in the molecule. The compound is not particularly limited as long as it is a compound, and specific examples thereof include diisocyanate compounds represented by the following formulas (I) to (X).

In the following formulas (I) to (X), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are independently hydrogen or alkyl having 1 to 7 carbon atoms.
X is an alkylene having 1 to 7 carbon atoms independently of each other.
Y is independently oxygen, sulfur, a linear or branched alkylene having 1 to 7 carbon atoms, -C (CF ₃ ) _2- or -SO _2- .

Among the above specific examples, the diisocyanate compounds represented by the formulas (V), (VI) and (VIII) are preferable because of their high solubility in a solvent. Further, when high transparency and heat resistance are required, 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 for example, Japanese Patent Application Laid-Open No. 2016-199694. Examples include the disclosed compounds.

An 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) norbornan, 2β, 5β-bis (isocyanate) norbornan, 2β, 6α-bis (isocyanate) norbornan, 2β, 6β-bis (isocyanate) norbornan, 2,6- Di (isocyanate methyl) furan, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, dicyclohexylmethane diisocyanate, 4,4-isopropyridenebis (cyclohexylisocyanate), cyclohexane Diisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethylmethanediisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanate-n-butylidene) pentaerythritol, diisocyanate dimerate, 3,8-bis (isocyanate methyl) Tricyclodecane, 3,9-bis (isocyanatemethyl) tricyclodecane, 4,8-bis (isocyanatemethyl) tricyclodecane, 4,9-bis (isocyanatemethyl) tricyclodecane, 1,5-diisocyanatedecalin, 2,7-Diisocyanate decalinate, 1,4-diisocyanate decalinate, 2,6-diisocyanate decalinate, dicyclohexylsulfide-4,4'-diisocyanate, tricyclothiaoctanediisocyanate.

As the diisocyanate compound described above, only one type may be used, or two or more types may be mixed and used.

2.2 Diamine compound <B>
The diamine compound <B> that can be used in the present invention is particularly limited as long as it is a diamine compound that is independently selected from an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton. It's not a thing. For example, a diamine compound disclosed in Japanese Patent Application Laid-Open No. 2014-65921 can be used.

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

In particular, the diamine compound <B> that can be used to impart high heat resistance is a diamine compound selected from an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton. Specific examples include 3,3'-diaminodiphenylsulfone, 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-xylylene diamine, p-xylylene diamine, 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.

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 the formulas (XIII-1) and (XIII-2).

For example, aliphatic diamines having a cyclic skeleton represented by the formulas (XIV-1) to (XIV-3) can be 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 formulas (XVI-13) to (XVI-19). Examples thereof include aromatic diamines having an ether bond.

For example, aromatic diamines represented by the formulas (XVII-1) to (XVII-4) and aromatic diamines having an ether bond represented by the formulas (XVII-5) and (XVII-6) can be mentioned.

For example, aromatic diamines represented by the formulas (XVIII-1) to (XVIII-7) and aromatic diamines having an ether bond represented by the formulas (XVIII-8) to (XVIII-11) can be mentioned.

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. Further, the diamine compound described above may be used alone or in combination of two or more.

3 Block Copolymer The block copolymer of the present invention contains a repeating unit represented by the formula (3), which is a double addition copolymer of the above-mentioned alternate copolymer 1 and the alternate copolymer 2. , A block copolymer having a weight average molecular weight of 50 to 1,000,000 and having either -NH _2- OH or -NCO end-sealed.

-[(Alternative copolymer 1)-(Alternative copolymer 2)]-Formula (3)
The alternating copolymer 1 and the alternating copolymer 2 are bonded via a urea bond or a urethane bond.

In the block copolymer of the present invention, when both ends of the alternate copolymer 1 are -NCO, both ends of the alternate copolymer 2 are -NH ₂ ; both ends of the alternate copolymer 1 are-. When it is OH, both ends of the alternate copolymer 2 are −NCO. Both of these terminal groups undergo a double addition reaction to form a urea bond or a urethane bond, resulting in the block copolymer of the present invention.

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

By changing the charging ratio (molar ratio) of the two types of monomers in the polyaddition reaction and the polycondensation reaction, an alternating copolymer having a terminal group corresponding to the monomer structure can be obtained, and the molecular weight can be arbitrarily obtained. Can also be controlled. This is Billmeyer. F. W. Step-Reaction (Condensation) Polymerization. In Textbook of Polymer Science; John Wiley &Sons; Singapore, 1994; pp35-39. It is described in.

Based on the above theory, when both ends of the alternate copolymer 1 constituting the block copolymer are -NCO, both ends of the alternate copolymer 2 must be -NH _2, and conversely, the alternate copolymers are co-located. When both ends of the polymer 1 are -OH, both ends of the alternate copolymer 2 need to be -NCO.

For example, in the case of producing a copolymer 1 having both ends of −NCO, the diisocyanate compound <A> is added in a step (step 1) in which the diisocyanate compound <A> and the diol compound < ^CS > are double-added. > May be used in a larger amount than the number of moles of the diol compound < ^CS >. For example, when the number of moles of the diisocyanate compound <A> is n1 and the number of moles of the diol compound < ^CS > is n2, the number of moles of each is 1.05 ≦ n1 / n2 ≦ 1.95. It is preferable to adjust to. In this way, the weight average molecular weight of the alternating copolymer 1 having −NCO at both ends can be adjusted in the range of 500,000 to 300,000.

In that case, since both ends of the alternating copolymer 2 are -NH ₂ , the diisocyanate compound <A'> and the diamine compound <B> are polymerized in the step (step 2). The number of moles of the diamine compound <B> may be larger than the number of moles of the diisocyanate compound <A'>. For example, when the number of moles of the diisocyanate compound <A'> is n1 and the number of moles of the diamine compound <B> is n2, the number of moles of each is 1.05 ≦ n2 / n1 ≦ 1.95. It is preferable to adjust to. In this way, the weight average molecular weight of the alternating copolymer ₂ having -NH ₂ at both ends can be adjusted in the range of 500,000 to 300,000.

Further, for example, in the case of producing a copolymer 1 in which both ends are −OH, the diol compound is added in a step (step 1) in which the diisocyanate compound <A> and the diol compound < ^CS > are double-added. The number of moles of < ^CS > may be larger than the number of moles of the diisocyanate compound <A>. For example, when the number of moles of the diisocyanate compound <A> is n1 and the number of moles of the diol compound < ^CS > is n2, the number of moles of each is 1.05 ≦ n2 / n1 ≦ 1.95. It is preferable to adjust to. In this way, the weight average molecular weight of the alternating copolymer 1 having −OH at both ends can be adjusted in the range of 500,000 to 300,000.

In that case, since both ends of the alternating copolymer 2 are -NCO, the diisocyanate compound <A'> and the diamine compound <B> are polymerized in the step (step 2). The number of moles of the compound <A'> may be larger than the number of moles of the diamine compound <B>. For example, when the number of moles of the diisocyanate compound <A'> is n1 and the number of moles of the diamine compound <B> is n2, the number of moles of each is 1.05 ≦ n1 / n2 ≦ 1.95. It is preferable to adjust to. In this way, the weight average molecular weight of the alternating copolymer 2 having −NCO at both ends can be adjusted in the range of 500,000 to 300,000.

Next, a method for producing a block copolymer will be described. Block copolymers
(I) A method for producing a block copolymer by introducing the alternating copolymer 1 obtained in step 1 and the alternating copolymer 2 obtained in step 2 into the same reaction vessel and performing a double addition reaction (i). ii) A method for producing a block copolymer by introducing the alternating copolymer 1 obtained in step 1 into a reaction vessel and then carrying out step 2 (iii) Alternating copolymer weight obtained in step 2. Method of producing a block copolymer by introducing the coalescence 2 into a reaction vessel and then carrying out step 1 (iv) After carrying out step 1 in the same container, block by continuously carrying out step 2. Method for Producing a Copolymer (v) A method for producing a block copolymer in a stepwise manner, which is exemplified in a method for producing a block copolymer by carrying out step 2 in the same container and then carrying out step 1 (hereinafter, step 1). Copolymerization method) is adopted. A block copolymer can be obtained by any of the step polymerization methods, but in order to obtain the desired properties, a plurality of step polymerization methods of one or more types may be combined, or a plurality of selected step polymerization methods may be used. A method of repeating the process may be adopted.

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

End groups of the block copolymer of the end groups present invention 6 block copolymer, -NH 2, but is either _-OH or -NCO, the end groups may be sealed. Since the ends are sealed, the storage stability of the block copolymer can be improved. To seal the end groups, the end sealants exemplified below can be used.

If end groups of -NCO, -NH ₂ group as a terminal blocking agent, -NH group, -OH group, -COOH group, it is possible to use a compound having an -SO2H group.

Specific examples of compounds having -NH ₂ groups that can be used as an end-capping agent include 1-aminobutane, 4-ethynylaniline, 3-ethynylaniline, propargylamine, 3-aminobutin, 4-aminobutin, and 5-aminopentin. , 4-Aminopentin, allylamine, 7-aminoheptin, m-aminostyrene, p-aminostyrene, m-amino-α-methylstyrene, 3-aminophenylacetylene, 4-aminophenylacetylene. Among these, 1-aminobutane is preferable from the viewpoint of excellent reactivity. Only one of these monoamine compounds may be used, or two or more of these monoamine compounds may be mixed and used.

Specific examples of compounds having a -NH group that can be used as an end-capping agent include dimethylamine, diethylamine, dipropylamine, dibutylamine, N-methylethylamine, N-methylpropylamine, N-methylbutylamine, and N. -Ethylpropylamine, N-ethylbutylamine, morpholine can be mentioned. Only one of these monoamine compounds may be used, or two or more of these monoamine compounds may be mixed and used.

Specific examples of the compound having a −OH group that can be used as an end-capping agent include a monoalcohol compound having 1 to 18 carbon atoms. Examples of monoalcohol compounds having 1 to 18 carbon atoms include linear monools (methanol, ethanol, n-propanol, n-butanol, pentanol, hexanol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, and tri). Decyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, etc.); Monools with branched chains (isopropanol, sec-, iso- or tert-butanol, neopentyl alcohol, 3-methyl-pentanol and 2-ethylhexanol) Etc.); Monools having a cyclic group having 6 to 10 carbon atoms [monool containing an alicyclic group (cyclohexanol, etc.), monool containing an aromatic ring (benzyl alcohol, etc.), etc.] can be mentioned. Further, specific examples of the compound having a -OH group include polymer monools (polyester monool, polyether monool, polyether ester monool, etc.), cellosolves and carbitols.

Of these, linear monool is preferred. Specifically, methanol, ethanol, n-propanol, n-butanol and the like.

Only one of these monoalcohol compounds may be used, or two or more of these monoalcohol compounds may be mixed and used.

When a compound having a −OH group is used as the terminal encapsulant, a general urethanization catalyst such as dibutyltin dilaurate can be used as the reaction catalyst. Urethaneization catalysts include, for example, various nitrogen-containing compounds such as N, N-dimethylaminoethyl ether, triethylamine, triethylenediamine, or N-methylmorpholine, and various types such as 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.

When the terminal reactive groups are -NH _{2 and} -OH, a compound having a -NCO group can be used as the terminal encapsulant.

Specific examples of the compound having a -NCO group that can be used as the terminal sealant include phenyl isocyanate, toluylene isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate. Only one of these monoisocyanate compounds may be used, or two or more of these monoisocyanate compounds may be mixed and used.

When a compound having a -NCO group is used as the terminal encapsulant, a general urethanization catalyst such as dibutyltin dilaurate can be used as the reaction catalyst. Urethaneization catalysts include, for example, various nitrogen-containing compounds such as N, N-dimethylaminoethyl ether, triethylamine, triethylenediamine, or N-methylmorpholine, and various types such as 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.

7 Reaction solvent The solvent used for producing the copolymer 1, the copolymer 2, and the block copolymer of the present invention is not particularly limited as long as these copolymers can be synthesized. Examples of the reaction solvent include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and the like. Ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, Diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropyl methyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl Ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether (1-methoxy- 2-Propanol), triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl -2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethyl Formamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethi Lu-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 Examples thereof include propyl alcohol, N, N-dimethylpropionamide, tetramethylurea, and dimethyl sulfoxide.

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 dimethyl sulfoxide because the block copolymer has good solubility and uniform polymerization proceeds.

Only one kind of these reaction solvents may be used, or two or more kinds may be mixed and used. Further, other solvents may be mixed and used in addition to the above reaction solvent.

When the reaction solvent is used in an amount of 100 parts by weight or more based on a total of 100 parts by weight of the diisocyanate compound <A>, the diisocyanate compound <A'>, the diamine compound <B>, and the diol compound < ^CS >, the reaction proceeds smoothly. Therefore, it is preferable. The reaction is preferably carried out at 0 ° C. to 150 ° C. for 0.2 to 20 hours.

8 Applications of block copolymer The block copolymer of the present invention can be used as a material for protecting an image display element from impact in the field of an image display element represented by a liquid crystal display or an organic EL display. .. For example, in a liquid crystal display, the film or coating material may be installed on the front surface or back surface of a cover glass or cover film, or on the front surface or back surface of a polarizing plate. Organic EL displays are becoming thinner and lighter due to flexibility, and the need for protecting elements from external forces such as impacts is becoming extremely high. Along with this, the block copolymer of the present invention is useful as a cover glass or a back surface of a cover film, a front surface or a back surface of a polarizing plate, a back film to be installed on an element body, or a coating material. It can also be used as a material inside an element such as a fill material, a sealing material, a dam material, a buffer material, and a flattening film.

In the field of automobiles, it is also useful as a material for protecting the exterior and interior of automobiles from impacts. For example, the external coating may be used as a paint protection film or a coating material to protect the external coating from scratches such as flying stones. Taking advantage of the excellent shock absorption of block copolymers, it may be used as a film or coating material to be installed on interlayer films, glazing, rear windows, rearview mirrors, sensors, etc. of laminated glass for automobiles.

Polyurea and polyurethane-based materials also have the potential to be used as biocompatible materials. Expected to be applied to medical devices that require blood compatibility, such as filtering by spinning such as electrospinning to make dialysis membranes, hollow fibers such as artificial cardiopulmonary, and coating on needles for infusion that are buried 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 for the purpose of preventing the window glass from scattering, for example, to prevent the window glass of a high-rise building from being destroyed, scattered and falling in the event of an earthquake or earthquake, or as a window for security purposes. It may be used to prevent the glass from breaking. Polyurea is known to enhance impact resistance by coating structural buildings, such as concrete and block walls, and can also be used as a coating material to prevent structural buildings from collapsing in the event of terrorism, earthquakes, or earthquakes. Good.

The polyurea-based alternating copolymer can also be used for the same purposes as the block copolymer.

9 Resin Composition The resin composition of the present invention is a composition containing the above block copolymer and a solvent that dissolves the block copolymer.

The solvent used in the resin composition of the present invention is not particularly limited as long as it can dissolve the block copolymer. For example, the reaction solvent used in the production of the block copolymer can be used as it is, or another solvent can be added and used as a mixed solvent.

Further, the block copolymer can be isolated as a solid component and then redissolved in a desired solvent for use. As a method for isolating the block copolymer, a solution containing the block copolymer and the reaction solvent is poured into a poor solvent for the block copolymer such as methanol, ethanol, and isopropyl ether to precipitate the block copolymer. Examples thereof include a method of separating the cells by filtering, washing, drying and the like. By performing such an operation, it is possible to remove the catalyst used in the production of the block copolymer.

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, dimethyl sulfoxide can be mentioned. Only one of these solvents may be used, or two or more of these solvents may be mixed and used. It is preferable to use these solvents because it is possible to prevent the precipitation of the polymer during film production and to produce a transparent and flat film.

The concentration of the block copolymer in the resin composition is not particularly limited. However, in terms of solubility and reactivity, it is preferably 10 to 80% by weight, more preferably 20 to 50% by weight.

The viscosity of the resin composition is preferably adjusted to an appropriate viscosity according to the method for 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, and is preferably adjusted to the range of 10 to 50,000 mPa · s.

Additives such as an ultraviolet absorber and a light stabilizer (HALS) may be further added to the resin composition of the present invention.

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

As UV absorbers, ADEKA Corporation's ADEKA STAB LA-46, ADEKA STAB LA-77Y, ADEKA STAB LA-63P, ADEKA STAB LA-72, ADEKA STAB LA-32, BASF's Tinubin 479, Tinubin 292, Tinubin 123, Tinubin 384-2, Chinubin 400 and the like can be mentioned.

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

Examples of the light stabilizer (HALS) include BASF TINUVIN (registered trademark) 5100 (neutral type general-purpose HALS) and TINUVIN292 (compound name: bis (1,2,2,6,6-pentamethyl-4-piperidinyl)). Sevacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate), TINUVIN152 (Compound name: 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,2) 6,6-Tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine), TINUVIN144 (Compound name: Bis (1,2,2,6,6-) Pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate), TINUVIN123 (compound name: decanodic acid, bis (2,2) Reaction product of 6,6-tetramethyl-1- (octyloxy) -4 piperidinyl) ester (in the presence of 1,1-dimethylethylhydroperoxide and octane)), TINUVIN111FDL (approximately 50%, TINUVIN622, compound name: (Butanidiate polymer (4-hydroxy-2,2,6,6-tetramethylpiperidinyl-yl) in the presence of ethanol), about 50%, CHIMASSORB119, compound name: N-N'-N "-N" '-Tetrax (4,5-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazine-2-yl) -4,7-diazadecan-1, 10-Diamine) or Adecastab LA series manufactured by Adeca Co., Ltd., specifically, LA-52 ((5) -6116), LA-57 ((5) -5555), LA-62 ((5)). -5711) and LA-67 ((5) -5755) can be mentioned. The numbers in parentheses are the existing chemical substance numbers stipulated by the Law Concerning the Examination and Manufacture of Chemical Substances in Japan (Chemical Substances Control Law).

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

In addition, if necessary, active energy ray sensitizers, polymerization inhibitors, waxes, plasticizers, leveling agents, surfactants, dispersants, defoamers, wettability improvers, antistatic agents, curing aids, etc. Various additives such as an additive that imparts antifouling property and low friction property, an additive that imparts scratch resistance, a heat stabilizer, a flame retardant, and a mold release agent can be mixed.

The resin composition of the present invention is a resin composition capable of forming a resin film having extremely excellent low temperature flexibility. Block copolymers are soluble in general-purpose organic solvents and have good heat resistance and mechanical properties.

The resin composition of the present invention may be a composition containing the block alternating copolymer and a solvent that dissolves the block copolymer.

10 Coating film The coating film of the present invention can be obtained by forming the resin composition of the present invention on a supporting base material or a structure by a method such as coating, printing, or casting, and then removing the solvent. The removing method may be, for example, drying, and the drying method is not particularly limited. Examples thereof include heating (hot air) drying, vacuum drying, steam drying, barrel drying, spin drying, suction drying and the like.

The drying method or drying conditions may be appropriately selected according to the type of solvent of the resin composition, the thickness and shape of the coating film, and the like. For example, in the case of heat drying, heat treatment using an air circulation type constant temperature oven, a heater using microwaves or far infrared rays, a hot plate, or the like can be mentioned. The drying conditions are not particularly limited as long as the solvent evaporates, 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, heating and drying may be performed in a nitrogen atmosphere or under reduced pressure.

The shape of the coating film from which the solvent has been removed may be determined according to the use described in the above-mentioned "Use of block copolymer". Alternatively, the solvent may be distilled off after applying the resin composition to the target portion.

Such a structure is preferable because a flat coating film is obtained.

11 Resin film The resin film of the present invention is formed by removing a solvent from the resin composition of the present invention into a film-like solid content. 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.

It is preferable to stack a plurality of layers because the impact absorption can be further enhanced by combining resin films having different strengths.

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. When it is 30 μm or more, it is preferable because it can be easily obtained as a film, and when it is 400 μm or less, it is preferable because the product can be made thinner.

In the case of two layers, the thickness of each film is preferably at least 1 to 999 μm, more preferably 10 to 490 μm, and particularly preferably 10 to 390 μm. When it is 10 μm or more, it is preferable because it can be easily obtained as a film, and when it is 390 μm or less, it is preferable because the product can be made thinner.

In the case of three layers, the thickness of each film is preferably at least 1 to 998 μm, more preferably 10 to 480 μm, and particularly preferably 10 to 380 μm. When it is 10 μm or more, it is preferable because it can be easily obtained as a film, and when it is 380 μm or less, it is preferable because the product can be made thinner.

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. When it is 30 μm or more, it is preferable because it can be easily obtained as a film, and when it is 400 μm or less, it is preferable because the product can be made thinner.

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 (coating method) other than the method using the applicator used in the examples may be used. Excellent surface smoothness can be obtained by using the coating method. Among the coating methods, the spin coating method and the bar coating method, which enable simple and homogeneous film formation when producing a small amount, 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 Examples thereof include a knife coating method, a curtain coating method, a rod coating method, and an inkjet method. Further, a method using various printing devices such as a letterpress printing method, an intaglio printing method, a lithographic printing method, and a stencil printing method can be mentioned. From these methods, it may be appropriately selected according to the required thickness, viscosity, curing conditions and the like.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

The meanings of the symbols used in the examples are as follows.
BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane (manufactured by Wakayama Seika Kogyo Co., Ltd.)
HXDI: 1,3-bis (isocyanate methyl) cyclohexane (manufactured by Mitsui Chemicals, Inc., product name; Takenate 600)
Cyraplane FM-441: Both-terminal hydroxyl-modified silicon compound, average molecular weight Mn; 1,000 (manufactured by JNC Co., Ltd.)
Silaplane FM-DA11: One-terminal hydroxyl-modified silicon compound, average molecular weight Mn; 1,000 (manufactured by JNC Co., Ltd.)
Morpholine: (manufactured by Tokyo Chemical Industry Co., Ltd.)
THF: Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph)
DMF: N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph)
DEF: N, N-diethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
PSt: Polystyrene (manufactured by PSS Polymer Standards Service)
Mw: Weight average molecular weight PDI (Mw / Mn): Molecular weight distribution index

Next, the analysis conditions in the production example and the example are shown.
<GPC>
Equipment: LC-2000Plus series manufactured by JASCO Corporation (detector: differential refractometer)
Solvent: THF / DMF = 1/1 (v / v), lithium bromide 10 mm mol / L content flow velocity: 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
<Total light transmittance, haze>
Equipment: Haze meter (NDH5000, manufactured by Nippon Denshoku Kogyo Co., Ltd.)
Analysis: JIS K7361 compliant <yellowness;YI>
Equipment: Spectral colorimeter (SD7000, manufactured by Nippon Denshoku Kogyo Co., Ltd.)
Analysis: JIS K7373 compliant <Dynamic viscoelasticity measurement>
Equipment: RSA-G2 (manufactured by TA Instruments Co., Ltd.)
Heating rate: 5 ° C / min
Frequency: 1Hz
Measurement temperature range: -80 ° C to 200 ° C
<Tensile test measurement>
Equipment: EZ-test (manufactured by Shimadzu Corporation)
Analysis: JIS K7161 compliant load cell: 200N
Tensile rate: 50 mm / min
Between chucks: 50 mm
Sample width: 10 mm

[Example 1] Synthesis of copolymer (1) / synthesis of HXDI-FMDA11 = 1.5: 1.0 Under a nitrogen atmosphere, HXDI (HXDI) was placed in a 200 mL three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel. 7.90 g), DEF (10.0 g), and silaplane FMDA11 (32.1 g) were introduced (solid content concentration 80 wt%). The reaction was initiated by heating to 120 ° C. using an oil bath (HXDI: FMDA11 = 1.5: 1.0). Then, the mixture was stirred for 5 hours while being maintained at 120 ° C. using an oil bath to obtain a transparent reaction solution. The Mw determined by GPC analysis of the reaction solution was 8,200, and the PDI was 2.2, and the desired copolymer (1) was obtained.

[Comparative Example 1] Synthesis of copolymer (2) / synthesis of HXDI-FM4411 = 1.5: 1.0 In a 1,000 mL three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. HXDI (32.7 g), DEF (40.0 g) and Cyraplane FMDA11 (127.3 g) were introduced (solid content concentration 80 wt%). The reaction was initiated by heating to 100 ° C. using an oil bath (HXDI: FM4411 = 1.5: 1.0, molar ratio). Then, the mixture was stirred for 3 hours while being maintained at 100 ° C. using an oil bath to obtain a transparent reaction solution. The Mw determined by GPC analysis of the reaction solution was 7,300 and the PDI was 2.0, and the desired copolymer (2) was obtained.

[Example 2] Synthesis of block copolymer (1) The copolymer (1) obtained in [Example 1] was placed in a three-necked flask (200 mL) equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. ) (Solid content concentration 80 wt%) (50.0 g) was introduced, and then DEF (21.4 g) and HXDI (3.16 g) were added. After heating to 100 ° C. using an oil bath, a solution prepared by dissolving BAPP (11.1 g) in DEF (35.7 g) was introduced into a dropping funnel. Then, the dropping funnel was promptly dropped to start the reaction, and after the dropping was completed, the dropping funnel was washed with DEF (14.3 g), and a washing liquid was added (solid content concentration 40 wt%). The mixture was stirred using an oil bath at 100 ° C. for 3 hours to react, and then morpholine (1.18 g) was added to quench the excess isocyanate group. The Mw determined by GPC analysis of the reaction solution was 118,500 and the PDI was 4.4, and a block copolymer (1), which is a polyurea-based polymer containing the structural unit of the target copolymer, was obtained.

[Comparative Example 2] Synthesis of Block Copolymer (2) The copolymer obtained in [Example 2] was placed in a three-necked flask (1,000 mL) equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. (2) (solid content concentration 80 wt%) (200.0 g) was introduced, and then DEF (28.9 g) and HXDI (13.1 g) were added. After heating to 100 ° C. using an oil bath, a solution prepared by dissolving BAPP (46.1 g) in DEF (202.2 g) was introduced into a dropping funnel. Then, the dropping funnel was promptly dropped to start the reaction, and after the dropping was completed, the dropping funnel was washed with DEF (57.8 g), and a washing liquid was added (solid content concentration 40 wt%). Then, the mixture was stirred using an oil bath at 100 ° C. for 3 hours to react, and then morpholine (4.77 g) was added to quench the excess isocyanate group. The Mw determined by GPC analysis of the reaction solution was 54,000 and the PDI was 3.1, and a block copolymer (2), which is a polyurea-based polymer containing the structural unit of the target copolymer, was obtained.

[Example 3] Preparation of resin film (1) A release film (product name: NSD-100, 100 μm, manufactured by Fujimori Kogyo Co., Ltd.) was used as a base material. The block copolymer (1) (concentration: 40%, solvent: DEF) synthesized in Example 2 was cast on a substrate, and a baker-type film applicator (product name: No. 510 Baker-type film applicator, Yasuda Co., Ltd.) By adjusting the scales on both sides of (manufactured by Seiki) to adjust the distance between the applicator and the base material, a coating film having a uniform film thickness was produced. After drying at 120 ° C. for 15 minutes, the release film was removed to obtain a single-layer resin film (1) having a film thickness of 50 μm.

[Comparative Example 3] Preparation of Resin Film (2)
A single-layer resin film (2) was obtained by a method according to Example 3 except that the block copolymer (2) was used instead of the block copolymer (1).

Table 1 shows the polymerization conditions of Example 1 and Comparative Example 1 and the molecular weight of the copolymer.

Table 1

Table 2 shows the polymerization conditions of Example 2 and Comparative Example 2 and the molecular weight of the block copolymer.

Table 2

Table 3 shows the measurement results of the total light transmittance, haze, and YI of the resin films (1) and (2) obtained in Example 3 and Comparative Example 3.

Table 3

Ratio of elastic modulus to storage elastic modulus at -20 ° C, 25 ° C and 100 ° C obtained from dynamic viscoelasticity measurements of resin films (1) and (2); (-20 ° C) / (25 ° C) results Is shown in Table 4, and the results of the tensile test measurement are shown in Table 5.

Table 4

Table 5

As is clear from the results in Table 1, the copolymer of Example 1 has excellent solubility in an organic solvent. Furthermore, from the results in Table 2, a block copolymer can be synthesized by using the obtained copolymer as a reactive oligomer. Furthermore, the obtained block copolymer is excellent in solubility in an organic solvent.

As is clear from the results in Table 4, the resin film (1) has a smaller ratio of storage elastic modulus at low temperature (-20 ° C) and room temperature (25 ° C) than the resin film (2), and is at room temperature. There is little change in elastic modulus at low temperatures. Since the elastic modulus does not increase at low temperature, it was clarified that it has excellent low temperature flexibility.

From the above, the copolymer of the present invention is soluble in a general-purpose organic solvent and is useful as a useful reactive oligomer. Furthermore, it is excellent in transparency and low temperature flexibility.

The copolymer of the present invention has particularly excellent properties of transparency, extensibility, flexibility, and heat resistance, and is also excellent in flexibility when used at low temperatures. It is useful as a highly elastic recovery material for flexible device applications in the field of electronic information materials. Furthermore, it is useful as a material that can be horizontally deployed in various applications such as automobiles, building materials, and life sciences.

Claims (18)

Diisocyanate compound <A> and, an addition polymer of a diol compound represented by the following formula (1) <C ^Si>, includes a repeating unit represented by the following formula (2), 500 weight average molecular weight A polyurethane-based alternating copolymer of 300,000.

(In equation (1)
n is an integer from 0 to 300
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen or alkyl with 1 to 30 carbon atoms, X ₁ , X ₂ , X ₃ and Each of X ₄ is a linear alkylene having 1 to 20 carbon atoms or a branched alkylene having 3 to 20 carbon atoms. )
-[(A)-(C ^Si )-]-Equation (2)
(A) and (C ^Si ) in the formula (2) are structural units corresponding to the diisocyanate compound <A> and the diol compound <C ^Si >. The polyurethane-based alternating copolymer according to claim 1, wherein the diol compound < ^CS > is a diol compound represented by the formula (1-1).

(In equation (1-1)
n is an integer from 0 to 300
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen or alkyl having 1 to 30 carbon atoms. ) The polyurethane alternating copolymer according to claim 1, wherein the diol compound < ^CS > is a diol compound represented by the formula (1-2).

(In equation (1-2)
n is an integer from 0 to 300
R ₉ and R ₁₀ are independently alkyl having 1 to 4 carbon atoms. ) The polyurethane alternating copolymer according to any one of claims 1 to 3, wherein the diisocyanate compound <A> is at least one kind of aliphatic diisocyanate having a cyclic structure in the molecule. The polyurethane alternating copolymer according to any one of claims 1 to 4, wherein the diisocyanate compound <A> is a compound represented by the following formulas (I) to (X).

(In formulas (I) to (X), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are independently hydrogen or alkyl having 1 to 7 carbon atoms.
X is an alkylene having 1 to 7 carbon atoms independently of each other.
Y is independently oxygen, sulfur, a linear or branched alkylene having 1 to 7 carbon atoms, -C (CF ₃ ) _2- or -SO _2- . ) The polyurethane alternating copolymer according to any one of claims 1 to 5, wherein the end is either -OH or -NCO which may be terminal-sealed. With the polyurethane alternating copolymer according to any one of claims 1 to 6;
Containing with a solvent that dissolves the polyurethane alternating copolymer;
Resin composition. The solvent used was propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, 4-methyl. Containing at least one of -2-pentanone, N, N-dimethylpropionamide, tetramethylurea, and dimethyl sulfoxide,
The resin composition according to claim 7. The following formula (1), which comprises dissolving the diisocyanate compound <A> and the diol compound < ^CS > represented by the following formula (1) in one or more kinds of organic solvents and obtaining a copolymer by solution polymerization. A method for producing a polyurethane alternating copolymer, which comprises the repeating unit represented by 2) and has a weight average molecular weight of 5 to 300,000.

(In equation (1)
n is an integer from 0 to 300
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen or alkyl with 1 to 30 carbon atoms, X ₁ , X ₂ , X ₃ and Each of X ₄ is a linear or branched alkylene having 1 to 20 carbon atoms. )
-[(A)-(C ^Si )-]-Equation (2)
(A) and (C ^Si ) in the formula (1) are structural units corresponding to the diisocyanate compound <A> and the diol compound <C ^Si >. It contains a structural unit which is a heavy addition copolymer of the alternating copolymer 1 and the alternating copolymer 2 represented by the following formula (3), has a weight average molecular weight of 5,000 to 300,000, and has both ends. A block copolymer in which is -NH ₂ or -NCO.
-[(Alternative copolymer 1)-(Alternative copolymer 2)]-Formula (3)
Alternating copolymer 1: Polyurethane alternating copolymer according to any one of claims 1 to 6 Alternating copolymer 2: A polyaddition copolymer of a diisocyanate compound <A'> and a diamine compound <B>. Therefore, the polyurea-based alternating copolymer represented by the following formula (4)-[(A')-(B)]-formula (4)
(A') is an aliphatic isocyanate structural unit having an intramolecular cyclic structure independently of each other;
(B) is a structural unit independently selected from an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton;
However, when both ends of the alternating copolymer 1 are -NCO, both ends of the alternating copolymer 2 are -OH;
When both ends of the alternating copolymer 1 are -NH ₂ , both ends of the alternating copolymer 2 are -NCO. Both ends of the alternating copolymer 1 are −OH, and both ends of the alternating copolymer 2 are −NCO.
The block copolymer according to claim 10. Both ends of the alternating copolymer 1 are -NCO, and both ends of the alternating copolymer 2 are -NH ₂ .
The block copolymer according to claim 10. The diisocyanate compound <A'> is a compound represented by the following formulas (I) to (X).
In the following formulas (I) to (X), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are independently hydrogen or alkyl having 1 to 7 carbon atoms.
X is an alkylene having 1 to 7 carbon atoms independently of each other.
Y is oxygen, sulfur, a linear or branched alkylene with 1-7 carbon atoms, -C (CF ₃ ) _2- or -SO _2- .
The block copolymer according to any one of claims 10 to 12.

The block copolymer according to any one of claims 10 to 13, wherein the ends may be end-sealed-OH, -NH ₂ or -NCO. With the block copolymer according to any one of claims 10 to 14;
Containing with a solvent that dissolves the block copolymer;
Resin composition. The solvent used was propylene glycol monomethyl ether (1-methoxy-2-propanol), N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, 4-methyl. Containing at least one of -2-pentanone, N, N-dimethylpropionamide, tetramethylurea, and dimethyl sulfoxide,
The resin composition according to claim 15. A solid content obtained by removing a solvent from the resin composition according to claim 15 or 16.
Coating film. It was formed from a solid content obtained by removing a solvent from the resin composition according to claim 15 or 16.
Resin film.