KR102377018B1 - Composition for forming polyurethane-based film, polyurethane-based film formed from the composition, and articles comprising the polyurethane-based film - Google Patents

Abstract

상기 식에서,
R₁ 및 R₂는 각각 독립적으로 수소원자, 할로겐, 치환 또는 비치환된 C₁ 내지 C₁₀ 알킬기, 치환 또는 비치환된 C₂ 내지 C₁₀ 알케닐기, 치환 또는 비치환된 C₂ 내지 C₁₀ 알키닐기, 치환 또는 비치환된 C₃ 내지 C₁₀ 시클로알킬기, 및 치환 또는 비치환된 C₆ 내지 C₂₀ 아릴기로 이루어진 군으로부터 선택된 어느 하나이다. 또한, 상기 폴리우레탄 필름 형성용 조성물로부터 유래된 자기 치유성, 특히 찢김으로부터의 자기 치유성이 개선된 폴리우레탄 필름을 제공한다.The present invention is a hydroxyl group-containing polymer; a first isocyanate group-containing compound; and an oligomer having a repeating unit derived from the compound of Formula 1 below,
The oligomer having a repeating unit derived from the compound of Formula 1 provides a composition for forming a polyurethane film, characterized in that it is a reaction product of a compound of Formula 1 and a second isocyanate group-containing compound:
[Formula 1]

In the above formula,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₂ to C ₁₀ alkenyl group, or a substituted or unsubstituted C ₂ to C ₁₀ alkyl Any one selected from the group consisting of a nyl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, and a substituted or unsubstituted C ₆ to C ₂₀ aryl group. In addition, there is provided a polyurethane film having improved self-healing properties, particularly, self-healing properties from tearing derived from the composition for forming a polyurethane film.

Description

Composition for forming a polyurethane film, a polyurethane film derived therefrom, and articles comprising the same

The present invention relates to a composition for forming a polyurethane film, a polyurethane film derived therefrom, and an article comprising the same.

Polyurethane is a representative compound constituting a film/coating formed on an automobile exterior part. The urethane bond of the polyurethane may be formed by combining a hydroxy (OH) group and an isocyanate (NCO) group.

The polyurethane may be divided into linear polyurethane and cross-linked polyurethane. As one method for producing a linear polyurethane, there is a method of condensation reaction of a polyol having two hydroxyl groups and a diisocyanate compound. In addition, as an exemplary method for producing a crosslinked polyurethane, a method of condensation reaction of a polyol having two or more hydroxyl groups and an isocyanate compound including three or more isocyanate groups, or a polyol having three or more hydroxyl groups and an isocyanate group There is a method of condensing an isocyanate compound containing two or more, but is not limited thereto.

It is known that the composition for forming the polyurethane, that is, the composition for forming a polyurethane film, is suitable for forming a coating film formed on automotive exterior parts in consideration of manufacturing cost, low temperature curability, and adhesiveness to a substrate.

As a conventional composition for forming a polyurethane film and a polyurethane film obtained therefrom, an elastically recoverable polyurethane (eg, Nissan Paint, Japan, Scratch Shield ^® ) is known, but this elastically recoverable polyurethane is self-healing by elasticity Although it has properties, it has a disadvantage in that it lacks self-healing properties from tears occurring outside the elastic limit. In order to solve this disadvantage, a method of improving self-healing properties by introducing an amine compound into the conventional composition for forming a polyurethane film has been proposed, but the composition for forming a polyurethane film in which the amine compound is introduced has strong reactivity within the composition. There was a problem that caused an unintended reaction to prevent the desired polyurethane film from being obtained.

In addition, the conventional polyurethane is manufactured using petrochemical-based materials, and there was a problem incompatible with the global trend in which environmental regulations are being strengthened. Therefore, there is a high demand for development of eco-friendly polyurethane based on sustainable materials.

In order to solve the above problems, one of the problems to be solved in the present invention is to provide a composition for forming a polyurethane film.

Another object to be solved in the present invention is to provide a polyurethane film derived from the composition for forming a polyurethane film having improved self-healing properties and mechanical properties.

Another one of the problems to be solved in the present invention is to provide an article including the polyurethane film.

In order to solve the above problems, according to an aspect of the present invention, there is provided a composition for forming a polyurethane film of the following embodiments.

A first embodiment is

a hydroxyl group-containing polymer; a first isocyanate group-containing compound; and an oligomer having a repeating unit derived from the compound of Formula 1 below,

The oligomer having a repeating unit derived from the compound of Formula 1 relates to a composition for forming a polyurethane film, characterized in that it is a reaction product of a compound of Formula 1 and a second isocyanate group-containing compound:

[Formula 1]

In the above formula,

R ₁ and R ₂ are each independently a hydrogen atom, a halogen, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₂ to C ₁₀ alkenyl group, or a substituted or unsubstituted C ₂ to C ₁₀ alkyl Any one selected from the group consisting of a nyl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, and a substituted or unsubstituted C ₆ to C ₂₀ aryl group.

In the second embodiment, according to the first embodiment,

The compound of Formula 1 may be isosorbide of Formula 2 below:

[Formula 2]

.

.

A third embodiment, according to the first or second embodiment,

The oligomer having a repeating unit derived from the compound of Formula 1 may be a compound of Formula 3 below:

[Formula 3]

In the above formula,

n is 1 to 200,

R ₁ and R ₂ are each independently a hydrogen atom, a halogen, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₂ to C ₁₀ alkenyl group, or a substituted or unsubstituted C ₂ to C ₁₀ alkyl Any one selected from the group consisting of a nyl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, and a substituted or unsubstituted C ₆ to C ₂₀ aryl group,

R is a substituted or unsubstituted C ₁ to C ₁₀ alkylene group, a substituted or unsubstituted C ₂ to C ₁₀ alkenylene group, a substituted or unsubstituted C ₂ to C ₁₀ alkynylene group, a substituted or unsubstituted C ₃ To C ₃₀ cycloalkylene group, a substituted or unsubstituted C ₃ to C ₃₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ to C ₃₀ arylene group, and a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group Any one selected from the group consisting of or a divalent linking group to which two or more of them are bonded.

In the fourth embodiment, according to the third embodiment,

The oligomer having a repeating unit derived from the compound of Formula 1 may be a compound of Formula 4 below:

[Formula 4]

In the above formula,

n is 1 to 200,

R is a substituted or unsubstituted C ₁ to C ₁₀ alkylene group, a substituted or unsubstituted C ₂ to C ₁₀ alkenylene group, a substituted or unsubstituted C ₂ to C ₁₀ alkynylene group, a substituted or unsubstituted C ₃ To C ₃₀ cycloalkylene group, a substituted or unsubstituted C ₃ to C ₃₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ to C ₃₀ arylene group, and a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group Any one selected from the group consisting of or a divalent linking group to which two or more of them are bonded.

A fifth embodiment, according to the third or fourth embodiment,

R is a substituted or unsubstituted, methylene group, ethylene group, propylene group, isopropylene group, butylene group, sec-butylene group, t-butylene group, n-butylene group, pentylene group, hexylene group, cyclopropylene group , cyclobutylene group, cyclopentylene group, cyclohexylene group, dicyclohexylenemethane group, isophoronylene group, phenylene group, benzylene group, diphenylenemethane group, diphenyleneethane group, xylene group, It may be any one selected from the group consisting of a tolylene group and a naphthalene group.

A sixth embodiment, according to any one of the third to fifth embodiments,

The oligomer having a repeating unit derived from the compound of Formula 1 may be a compound of Formulas 5 to 16 below:

[Formula 5]

,

,

[Formula 6]

,

,

[Formula 7]

,

,

[Formula 8]

,

,

[Formula 9]

,

,

[Formula 10]

,

,

[Formula 11]

,

,

[Formula 12]

,

,

[Formula 13]

,

,

[Formula 14]

,

,

[Formula 15]

, 및

, and

[Formula 16]

In the above formula,

n is 1 to 200,

R ₁ and R ₂ are each independently a hydrogen atom, a halogen, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₂ to C ₁₀ alkenyl group, or a substituted or unsubstituted C ₂ to C ₁₀ alkyl Any one selected from a nyl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, and a substituted or unsubstituted C ₆ to C ₂₀ aryl group.

The seventh embodiment, according to the sixth embodiment,

The oligomer having a repeating unit derived from the compound of Formula 1 may be a compound of Formulas 17 to 28 below:

[Formula 17]

,

,

[Formula 18]

,

,

[Formula 19]

,

,

[Formula 20]

,

,

[Formula 21]

,

,

[Formula 22]

,

,

[Formula 23]

,

,

[Formula 24]

,

,

[Formula 25]

,

,

[Formula 26]

,

,

[Formula 27]

, 및

, and

[Formula 28]

In the above formula,

n is 1 to 200;

The eighth embodiment, according to any one of the first to seventh embodiments,

The hydroxyl group-containing polymer is a hydroxyl group-containing polyacrylate-based compound; hydroxyl group-containing polymethacrylate-based compounds; hydroxyl group-containing polystyrene-based compounds; a polymer including a repeating unit derived from two or more monomers selected from a hydroxyl group-containing acrylate-based monomer, a hydroxyl group-containing methacrylate-based monomer, and a hydroxyl group-containing styrene-based monomer; Or it may include two or more of them.

A ninth embodiment, according to any one of the first to eighth embodiments,

The oligomer having a repeating unit derived from the compound of Formula 1 may be included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the hydroxyl group-containing polymer.

The tenth embodiment, according to any one of the first to ninth embodiments,

The hydroxyl group-containing polymer may have a number average molecular weight in the range of 100 to 1,000,000.

An eleventh embodiment, according to any one of the first to tenth embodiments,

The ratio of the total number of isocyanate groups in the isocyanate group-containing compound to the total number of hydroxyl groups that are the sum of the hydroxyl groups in the hydroxyl group-containing polymer and the hydroxyl groups in the oligomer having a repeating unit derived from the compound of Formula 1 (isocyanate groups) / hydroxy group number ratio) may be 0.5 to 1.5.

In order to solve the above problems, according to one aspect of the present invention, there is provided a polyurethane film of the following embodiment.

The twelfth embodiment is

It relates to a polyurethane film derived from the composition for forming a polyurethane film according to any one of the first to eleventh embodiments.

In order to solve the above problems, according to one aspect of the present invention, there is provided an article comprising the polyurethane film of the following embodiment.

The thirteenth embodiment is

Board; and

It is located on at least one surface of the substrate and relates to an article comprising the polyurethane film according to the twelfth embodiment.

The fourteenth embodiment, according to the thirteenth embodiment,

The substrate may be an article in which the substrate is a metal substrate, a glass substrate, or a polymer substrate.

As described above, the composition for forming a polyurethane film according to an embodiment of the present invention has a repeating unit derived from the compound of Formula 1 in addition to the hydroxyl group-containing polymer and the isocyanate group-containing compound that forms the polyurethane. By further including an oligomer, it is possible to form a polyurethane film having improved self-healing properties and mechanical properties.

In addition, the polyurethane film obtained from the composition for forming a polyurethane film according to an embodiment of the present invention is a futuristic smart coating technology capable of recovering surface damage caused by external stimuli by itself, and continuous exposure to extreme external environments is Excellent quality improvement can be expected in the field of coating for transportation equipment such as automobiles, aircraft, ships, etc., and in the field of preservation of the appearance of electronic products such as mobile phones, tablet PCs, and displays.

1 is a photograph evaluating the self-healing properties of the polyurethane film obtained in Example 1.
Figure 2 is a photograph evaluating the self-healing properties of the polyurethane film obtained in Comparative Example 1.
3 is a photograph evaluating the surface strength of the polyurethane film obtained in Example 1.
4 is a photograph evaluating the surface strength of the polyurethane film obtained in Comparative Example 2.

Hereinafter, the present invention will be described in detail. Prior to this, the terms or words used in the present specification and claims should not be construed as being limited to conventional or dictionary meanings, and the inventor should properly understand the concept of the term in order to best describe his invention. Based on the principle that it can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Accordingly, the configuration shown in the embodiments described in the present specification is merely the most preferred embodiment of the present invention and does not represent all the technical spirit of the present invention, so various equivalents that can be substituted for them at the time of the present application It should be understood that there may be variations and variations.

In this specification, terms such as “first”, “second”, etc. are used to distinguish one component from another, and each component is not limited by the terms.

The composition for forming a polyurethane film according to an aspect of the present invention

a hydroxyl group-containing polymer; a first isocyanate group-containing compound; and an oligomer having a repeating unit derived from the compound of Formula 1 below,

The oligomer having a repeating unit derived from the compound of Formula 1 is a composition for forming a polyurethane film, characterized in that it is a reaction product of a compound of Formula 1 and a second isocyanate group-containing compound:

[Formula 1]

In the above formula,

R ₁ and R ₂ are each independently a hydrogen atom, a halogen, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₂ to C ₁₀ alkenyl group, or a substituted or unsubstituted C ₂ to C ₁₀ alkyl Any one selected from the group consisting of a nyl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, and a substituted or unsubstituted C ₆ to C ₂₀ aryl group.

In one embodiment of the present invention, the hydroxyl group-containing polymer is a hydroxyl group-containing polyacrylate-based compound; hydroxyl group-containing polymethacrylate-based compounds; hydroxyl group-containing polystyrene-based compounds; a polymer including a repeating unit derived from two or more monomers selected from a hydroxyl group-containing acrylate-based monomer, a hydroxyl group-containing methacrylate-based monomer, and a hydroxyl group-containing styrene-based monomer; Or it may include two or more of these.

In this case, the hydroxyl group-containing acrylate-based monomer, the hydroxyl group-containing methacrylate-based monomer, and the hydroxyl group-containing styrene-based monomer are, respectively, an acrylate-based monomer, a methacrylate-based monomer, and styrene It means that at least one or more hydrogens of the system monomer are substituted with a hydroxyl group (OH group). In addition, a hydroxyl group-containing polyacrylate-based compound; hydroxyl group-containing polymethacrylate-based compounds; The hydroxyl group-containing polystyrene-based compound is a homopolymer of each of these hydroxyl group-containing acrylate monomers, hydroxyl group-containing methacrylate monomers, and hydroxyl group-containing styrenic monomers, or It refers to a copolymer further comprising a repeating unit derived from another monomer other than the group-containing acrylate-based monomer, the hydroxyl group-containing methacrylate-based monomer, and the hydroxyl group-containing styrene-based monomer.

In one embodiment of the present invention, in the composition for forming a polyurethane film, the mole % of the repeating unit having a hydroxyl group in the hydroxyl group-containing polymer corresponds to one factor determining the mechanical properties of the polyurethane film, and the purpose of use may vary, and may be in the range of more than 0 mol% and within 100 mol%, 1 mol% to 100 mol%, and 1 mol% to 50 mol%.

The hydroxyl group-containing polymer may have a number average molecular weight in the range of 100 to 1,000,000, or 100 to 100,000, or 100 to 10,000, or 100 to 5,000. When the number average molecular weight of the polymer satisfies the above range, it may be advantageous in terms of mechanical properties of the coating and film. The number average molecular weight of the hydroxyl group-containing polymer may be measured using gel permeation chromatography.

In one embodiment of the present invention, the first isocyanate group-containing compound may be an aliphatic, aromatic, alicyclic, or aromatic aliphatic compound containing two or more isocyanate groups in its molecular structure.

Among the first isocyanate group-containing compounds, the aliphatic isocyanate group-containing compound is ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), octamethylene diisocyanate, nonamethylene diisocyanate, dodecamethylene. Diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4, 4-Trimethyl hexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatemethylcaproate, bis(2-isocyanate) Ethyl) fumarate, bis (2-isocyanate ethyl) carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, 1,3,5-hexamethylene triisocyanate, 1,8-diisocyanate Ito-4-isocyanate, bis(isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-ω, ω'-diisocyanate, lysine diisocyanato methyl ester, lysine triisocyanate, 2-iso Cyanatoethyl-2,6-diisocyanatoethyl-2,6-diisocyanato hexanoate, 2-isocyanatopropyl-2,6-diisocyanato hexanoate, 2,6 -di(isocyanatomethyl)furan, 1,3-bis(6-isocyanatohexyl)-uretidine-2,4-dione, 1,3,5-tris(6-isocyanato) hexyl) isocyanurate, or two or more of these.

Among the first isocyanate group-containing compounds, the aromatic isocyanate group-containing compound is phenylene 1,4-diisocyanate, tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate (TDI), naphthylene 1,5 -diisocyanate, diphenylmethane 2,2'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenylmethane 4,4'-diisocyanate (MDI), polymeric diphenylmethane diisocyanate (pMDI) or Two or more of these may be included.

Among the first isocyanate group-containing compounds, the alicyclic isocyanate group-containing compound is isophorone diisocyanate (IPDI), 1,4-cyclohexane diisocyanate, methylene bis(4-cyclohexyl) diisocyanate, 4,4'-dicy Chlohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2-isocyanateethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate , 2,6-norbornane diisocyanate, 2,2-dimethyl dicyclohexylmethane diisocyanate, bis(4-isocyanato-n-butylidene)pentaerythritol, dimer acid diisocyanate, 2-iso Cyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocy Anatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl -Bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2 -isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3 -(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.1.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanato Propyl)-5-(2-isocyanatoethyl)-bicyclo[2.1.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2- isocyanatoethyl)-bicyclo[2.2.1]-heptane, norbornane bis(isocyanatomethyl), or two or more thereof.

Among the first isocyanate group-containing compounds, the aromatic aliphatic isocyanate group-containing compound is 1,3-bis(isocyanatomethyl)benzene (m-xylene diisocyanate, m-XDI), 1,4-bis(isocyane) Itomethyl) benzene (p-xylene diisocyanate, p-XDI), 1,3-bis (2-isocyanato propan-2-yl) benzene (m-tetramethyl xylene diisocyanate, m-TMXDI), 1 ,3-bis(isocyanatomethyl)-4-methylbenzene, 1,3-bis(isocyanatomethyl)-4-ethylbenzene, 1,3-bis(isocyanatomethyl)-5- Methylbenzene, 1,3-bis(isocyanatomethyl)-4,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,5-dimethylbenzene, 1,4-bis(iso Cyanatomethyl)-2,3,5,6-tetramethylbenzene, 1,3-bis(isocyanatomethyl)-5-tert-butyl benzene, 1,3-bis(isocyanatomethyl) -4-chlorobenzene, 1,3-bis (isocyanatomethyl) -4,5-dichlorobenzene, 1,3-bis (isocyanatomethyl) -2,4,5,6-tetrachlorobenzene , 1,4-bis(isocyanatomethyl)-2,3,5,6-tetrachlorobenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetrabromo Benzene, 1,4-bis(2-isocyanatoethyl)benzene, 1,4-bis(isocyanatomethyl)naphthalene, xylylene diisocyanate, bis(isocyanatoethyl)benzene, bis( Isocyanatopropyl)benzene, α,α,α',α'-tetramethyl xylylene diisocyanate, bis(isocyanatobutyl)benzene, bis(isocyanatopropyl)naphthalene, bis(isocy anatomethyl) diphenyl ether, bis(isocyanatoethyl)phthalate, or two or more of these.

In the present invention, the oligomer having a repeating unit derived from the compound of Formula 1 is a reaction product formed by reacting the compound of Formula 1 with an isocyanate group-containing compound (second isocyanate group-containing compound) containing two or more isocyanate groups. it means:

[Formula 1]

In the above formula,

R ₁ and R ₂ are each independently a hydrogen atom, a halogen, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₂ to C ₁₀ alkenyl group, or a substituted or unsubstituted C ₂ to C ₁₀ alkyl Any one selected from the group consisting of a nyl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, and a substituted or unsubstituted C ₆ to C ₂₀ aryl group.

, 시아노기, 치환 또는 비치환된 아미노기(-NH₂, -NH(R), -N(R')(R''), R'과 R"은 서로 독립적으로 탄소수 1 내지 10의 알킬기임), 아미디노기, 히드라진, 또는 히드라존기 카르복실기, 술폰산기, 인산기, C₁ 내지 C₂₀의 알킬기, C₁ 내지 C₂₀의 할로겐화된 알킬기, C₁ 내지 C₂₀의 알케닐기, C₁ 내지 C₂₀의 알키닐기, C₁ 내지 C₂₀의 헤테로알킬기, C₆ 내지 C₂₀의 아릴기, C₆ 내지 C₂₀의 아릴알킬기, C₆ 내지 C₂₀의 헤테로아릴기, 또는 C₆ 내지 C₂₀의 헤테로아릴알킬기로 치환될 수 있다.A substituted or unsubstituted C ₁ to C ₁₀ alkyl group described herein means a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 10 carbon atoms, and such an alkyl group is a substituted or unsubstituted C ₁ to C ₅ It may be an alkyl group, or a substituted or unsubstituted C ₁ to C ₃ alkyl group. For example, at least one hydrogen atom included in the alkyl group is a halogen atom, a hydroxyl group, -SH, a nitro group,

, cyano group, substituted or unsubstituted amino group (-NH ₂ , -NH(R), -N(R')(R''), R' and R" are each independently an alkyl group having 1 to 10 carbon atoms) , amidino group, hydrazine, or hydrazone group carboxyl group, sulfonic acid group, phosphoric acid group, C ₁ to C ₂₀ alkyl group, C ₁ to C ₂₀ halogenated alkyl group, C ₁ to C ₂₀ alkenyl group, C ₁ to C ₂₀ alkynyl group, C ₁ to C ₂₀ heteroalkyl group, C ₆ to C ₂₀ aryl group, C ₆ to C ₂₀ arylalkyl group, C ₆ to C ₂₀ heteroaryl group, or C ₆ to C ₂₀ heteroarylalkyl group can be replaced with

A substituted or unsubstituted C ₂ to C ₁₀ alkenyl group refers to a substituted or unsubstituted straight-chain or branched aliphatic hydrocarbon group having 2 to 10 carbon atoms having a carbon-carbon double bond, and such an alkenyl group is a substituted or unsubstituted It may be a C ₂ to C ₆ alkenyl group, or a substituted or unsubstituted C ₂ to C ₄ alkenyl group. For example, one or more hydrogen atoms included in the alkenyl group may be substituted with the same substituents as in the case of the alkyl group.

A substituted or unsubstituted C ₂ to C ₁₀ alkynyl group refers to a substituted or unsubstituted straight-chain or branched aliphatic hydrocarbon group having 2 to 10 carbon atoms having a carbon-carbon triple bond, and such alkynyl group is a substituted or unsubstituted It may be a C ₂ to C ₆ alkynyl group, or a substituted or unsubstituted C ₂ to C ₄ alkynyl group. For example, one or more hydrogen atoms included in the alkynyl group may be substituted with the same substituents as in the case of the alkyl group.

A substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group means a substituted or unsubstituted monovalent monocyclic system having 3 to 10 carbon atoms, and may be a substituted or unsubstituted C ₃ to C ₆ cycloalkyl group, Or it may be a substituted or unsubstituted C ₅ to C ₆ cycloalkyl group. For example, one or more hydrogen atoms included in the cycloalkyl group may be substituted with the same substituents as in the case of the alkyl group.

A substituted or unsubstituted C ₆ to C ₂₀ aryl group is used alone or in combination to mean a substituted or unsubstituted carbocyclic aromatic system having 6 to 20 carbon atoms containing one or more rings, wherein the rings are attached together in a pendant manner. or can be fused. The aryl group may be a substituted or unsubstituted C ₆ to C ₁₈ aryl group, a substituted or unsubstituted C ₆ to C ₁₅ aryl group, and may include a phenyl group, a naphthyl group, and a biphenyl group. For example, one or more hydrogen atoms included in the aryl group may be substituted with the same substituents as in the case of the alkyl group.

Since the oligomer having a repeating unit derived from the compound of Formula 1 includes a hydroxyl group in a molecule, it may react with the first isocyanate group-containing compound together with the hydroxyl group-containing polymer to form a urethane bond.

In general, as the self-healing performance of polyurethane increases, the mechanical properties tend to weaken. When the compound of Formula 1 is included alone in the composition for forming a polyurethane, the compound of Formula 1 is randomly present in the finally produced polyurethane film. On the other hand, when an oligomer having a repeating unit derived from the compound of Formula 1 is included in the composition for forming a polyurethane, a hydroxyl functional group exists in the oligomer in the form of a cluster, so that it can strongly interact with the urethane even within a narrow range. A polyurethane film having improved self-healing ability can be prepared compared to including the compound of Formula 1 alone in the composition for forming polyurethane.

In addition, when the oligomer having a repeating unit derived from the compound of Formula 1 is included in the composition for forming a polyurethane, polyurethane with enhanced mechanical properties compared to including the compound of Formula 1 alone in the composition for forming a polyurethane Films can be made. That is, the composition for forming a polyurethane comprising an oligomer having a repeating unit derived from the compound of Formula 1 can prepare a polyurethane film with enhanced mechanical properties while improving self-healing ability.

Specifically, in one embodiment of the present invention, the compound of Formula 1 may be isosorbide of Formula 2 below:

[Formula 2]

.

.

Since the child carbide includes a hydroxyl group in the molecule, it can react with an isocyanate group-containing compound (a second isocyanate group-containing compound) to form a child carbide oligomer.

In one embodiment of the present invention, the second isocyanate group-containing compound may be of the same type as the first isocyanate group-containing compound, or may be a different type.

In one embodiment of the present invention, the second isocyanate group-containing compound may be an isocyanate group-containing compound including two or more isocyanate groups.

In one embodiment of the present invention, the second isocyanate group-containing compound may be an aliphatic, aromatic, alicyclic, or aromatic aliphatic compound containing two or more isocyanate groups in its molecular structure.

Among the second isocyanate group-containing compounds, the aliphatic isocyanate group-containing compound is ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HMDI), octamethylene diisocyanate, nonamethylene diisocyanate, dodecamethylene. Diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4, 4-Trimethyl hexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatemethylcaproate, bis(2-isocyanate) Ethyl) fumarate, bis (2-isocyanate ethyl) carbonate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, 1,3,5-hexamethylene triisocyanate, 1,8-diisocyanate Ito-4-isocyanate, bis(isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-ω, ω'-diisocyanate, lysine diisocyanato methyl ester, lysine triisocyanate, 2-iso Cyanatoethyl-2,6-diisocyanatoethyl-2,6-diisocyanato hexanoate, 2-isocyanatopropyl-2,6-diisocyanato hexanoate, 2,6 -di(isocyanatomethyl)furan, 1,3-bis(6-isocyanatohexyl)-uretidine-2,4-dione, 1,3,5-tris(6-isocyanato) hexyl) isocyanurate, or two or more of these.

Among the second isocyanate group-containing compounds, the aromatic isocyanate group-containing compound is phenylene 1,4-diisocyanate, tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate (TDI), naphthalene 1,5- diisocyanate, diphenylmethane 2,2'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenylmethane 4,4'-diisocyanate (MDI), polymeric diphenylmethane diisocyanate (pMDI), or Two or more of these may be included.

Among the second isocyanate group-containing compounds, the alicyclic isocyanate group-containing compound is isophorone diisocyanate (IPDI), 1,4-cyclohexane diisocyanate, methylene bis(4-cyclohexyl) diisocyanate, 4,4'-dicy Chlohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2-isocyanateethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate , 2,6-norbornane diisocyanate, 2,2-dimethyl dicyclohexylmethane diisocyanate, bis(4-isocyanato-n-butylidene)pentaerythritol, dimer acid diisocyanate, 2-iso Cyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocy Anatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl -Bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2 -isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3 -(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.1.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanato Propyl)-5-(2-isocyanatoethyl)-bicyclo[2.1.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2- isocyanatoethyl)-bicyclo[2.2.1]-heptane, norbornane bis(isocyanatomethyl), or two or more thereof.

Among the second isocyanate group-containing compounds, the aromatic aliphatic isocyanate group-containing compound is 1,3-bis(isocyanatomethyl)benzene (m-xylene diisocyanate, m-XDI), 1,4-bis(isocyane) Itomethyl) benzene (p-xylene diisocyanate, p-XDI), 1,3-bis (2-isocyanato propan-2-yl) benzene (m-tetramethyl xylene diisocyanate, m-TMXDI), 1 ,3-bis(isocyanatomethyl)-4-methylbenzene, 1,3-bis(isocyanatomethyl)-4-ethylbenzene, 1,3-bis(isocyanatomethyl)-5- Methylbenzene, 1,3-bis(isocyanatomethyl)-4,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,5-dimethylbenzene, 1,4-bis(iso Cyanatomethyl)-2,3,5,6-tetramethylbenzene, 1,3-bis(isocyanatomethyl)-5-tert-butyl benzene, 1,3-bis(isocyanatomethyl) -4-chlorobenzene, 1,3-bis (isocyanatomethyl) -4,5-dichlorobenzene, 1,3-bis (isocyanatomethyl) -2,4,5,6-tetrachlorobenzene , 1,4-bis(isocyanatomethyl)-2,3,5,6-tetrachlorobenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetrabromo Benzene, 1,4-bis(2-isocyanatoethyl)benzene, 1,4-bis(isocyanatomethyl)naphthalene, xylylene diisocyanate, bis(isocyanatoethyl)benzene, bis( Isocyanatopropyl)benzene, α,α,α',α'-tetramethyl xylylene diisocyanate, bis(isocyanatobutyl)benzene, bis(isocyanatopropyl)naphthalene, bis(isocy anatomethyl) diphenyl ether, bis(isocyanatoethyl)phthalate, or two or more of these.

In one embodiment of the present invention, in the oligomer having a repeating unit derived from the compound of Formula 1, the molar ratio of the compound of Formula 1 to the second isocyanate group-containing compound is 10:1 to 10:9, or 10:1 to 10 : May be 5.

In one embodiment of the present invention, the oligomer having a repeating unit derived from the compound of Formula 1 may be a compound of Formula 3 below:

[Formula 3]

In the above formula,

n is 1 to 200,

R ₁ and R ₂ are each independently a hydrogen atom, a halogen, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₂ to C ₁₀ alkenyl group, or a substituted or unsubstituted C ₂ to C ₁₀ alkyl Any one selected from the group consisting of a nyl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, and a substituted or unsubstituted C ₆ to C ₂₀ aryl group,

R is a substituted or unsubstituted C ₁ to C ₁₀ alkylene group, a substituted or unsubstituted C ₂ to C ₁₀ alkenylene group, a substituted or unsubstituted C ₂ to C ₁₀ alkynylene group, a substituted or unsubstituted C ₃ To C ₃₀ cycloalkylene group, a substituted or unsubstituted C ₃ to C ₃₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ to C ₃₀ arylene group, and a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group Any one selected from the group consisting of or a divalent linking group to which two or more of them are bonded.

A substituted or unsubstituted C ₁ to C ₁₀ alkylene group described herein refers to a substituted or unsubstituted straight-chain or branched saturated divalent hydrocarbon moiety having 1 to 10 carbon atoms, and such an alkylene group is a substituted Or it may be an unsubstituted C ₁ to C ₆ alkylene group, or a substituted or unsubstituted C ₁ to C ₃ alkylene group. For example, one or more hydrogen atoms included in the alkylene group may be substituted with the same substituents as in the case of the aforementioned alkyl group.

A substituted or unsubstituted C ₂ to C ₁₀ alkenylene group refers to a substituted or unsubstituted straight-chain or branched aliphatic divalent hydrocarbon group having 2 to 10 carbon atoms having a carbon-carbon double bond, and such an alkenylene group is a substituted or unsubstituted It may be a cyclic C ₂ to C ₆ alkenylene group, or a substituted or unsubstituted C ₂ to C ₄ alkenylene group. For example, one or more hydrogen atoms included in the alkenylene group may be substituted with the same substituents as in the case of the alkyl group.

A substituted or unsubstituted C ₂ to C ₁₀ alkynylene group refers to a substituted or unsubstituted straight-chain or branched aliphatic divalent hydrocarbon group having 2 to 10 carbon atoms having a carbon-carbon triple bond, and such alkynylene group is a substituted or unsubstituted It may be a cyclic C ₂ to C ₆ alkynylene group, or a substituted or unsubstituted C ₂ to C ₄ alkynylene group. For example, one or more hydrogen atoms included in the alkynylene group may be substituted with the same substituents as in the case of the alkyl group.

A substituted or unsubstituted C ₃ to C ₃₀ cycloalkylene group means a substituted or unsubstituted divalent monocyclic system having 3 to 30 carbon atoms, and such a cycloalkylene group is a substituted or unsubstituted C ₃ to C ₁₅ It may be a cycloalkylene group, a substituted or unsubstituted C ₃ to C ₁₂ cycloalkylene group, or a substituted or unsubstituted C ₃ to C ₆ cycloalkylene group. For example, one or more hydrogen atoms included in the cycloalkylene group may be substituted with the same substituents as in the case of the alkyl group.

A substituted or unsubstituted C ₃ to C ₃₀ heterocycloalkylene group contains 1, 2 or 3 heteroatoms selected from N, O, P or S, and the remaining ring atoms are C 3 to 30 ring atoms, preferably preferably 3 to 10, more preferably 3 to 6 substituted or unsubstituted divalent monocyclic systems. For example, one or more hydrogen atoms included in the heterocycloalkylene group may be substituted with the same substituents as in the case of the alkyl group.

A substituted or unsubstituted C ₆ to C ₃₀ arylene group is used alone or in combination to mean a substituted or unsubstituted divalent carbocyclic aromatic system having 6 to 30 carbon atoms including one or more rings, wherein the rings are pendant method may be attached or fused together. The arylene group may be a substituted or unsubstituted C ₆ to C ₁₈ arylene group, or a substituted or unsubstituted C ₆ to C ₁₅ arylene group, and may include a phenyl group, a naphthyl group, and a biphenyl group. For example, one or more hydrogen atoms included in the aryl group may be substituted with the same substituents as in the case of the alkyl group.

A substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group includes 1, 2 or 3 hetero atoms selected from N, O, or S, and the remaining ring atoms are C 3 to 30 substituted or unsubstituted ring atoms means a divalent monocyclic or bicyclic aromatic radical. For example, one or more hydrogen atoms included in the heteroaryl group may be substituted with the same substituents as in the case of the alkyl group.

R is the substituted or unsubstituted C ₁ to C ₁₀ alkylene group, substituted or unsubstituted C ₂ to C ₁₀ alkenylene group, substituted or unsubstituted C ₂ to C ₁₀ alkynylene group, substituted or unsubstituted C ₃ to C ₃₀ cycloalkylene group, substituted or unsubstituted C ₃ to C ₃₀ heterocycloalkylene group, substituted or unsubstituted C ₆ to C ₃₀ arylene group, and substituted or unsubstituted C ₅ to C ₃₀ heteroarylene It may be any one divalent linking group selected from the group consisting of groups, or may be a divalent linking group to which two or more of them are bonded. In this case, that R is a divalent linking group to which two or more of the substituents are bonded means, for example, 'cycloalkylene group-alkylene group-cycloalkylene group', or 'arylene group-alkylene group-arylene group', etc. It refers to a divalent linking group of various structures in which two or more substituents are bonded.

In one embodiment of the present invention, R is a substituted or unsubstituted, methylene group, ethylene group, propylene group, isopropylene group, butylene group, sec-butylene group, t-butylene group, n-butylene group, pentylene group , hexylene group, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, dicyclohexylenemethane group, isophoronylene group, phenylene group, benzylene group, diphenylenemethane group, di It may be any one selected from the group consisting of a phenyleneethane group, a xylene group, a tolylene group, and a naphthalene group.

In one embodiment of the present invention, n may be 1 to 100, or 1 to 50.

The number average molecular weight of the compound of Formula 3 may be measured using gel permeation chromatography.

The compound of Formula 3 may be, for example, a compound of Formula 4 below:

[Formula 4]

In the above formula,

n is 1 to 200,

R is a substituted or unsubstituted C ₁ to C ₁₀ alkylene group, a substituted or unsubstituted C ₂ to C ₁₀ alkenylene group, a substituted or unsubstituted C ₂ to C ₁₀ alkynylene group, a substituted or unsubstituted C ₃ To C ₃₀ cycloalkylene group, a substituted or unsubstituted C ₃ to C ₃₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ to C ₃₀ arylene group, and a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group Any one selected from the group consisting of or a divalent linking group to which two or more of them are bonded.

In one embodiment of the present invention, n may be 1 to 100, or 1 to 50.

In one embodiment of the present invention, the oligomer having a repeating unit derived from the compound of Formula 1 may be a compound of Formulas 5 to 16 below:

[Formula 5]

,

,

[Formula 6]

,

,

[Formula 7]

,

,

[Formula 8]

,

,

[Formula 9]

,

,

[Formula 10]

,

,

[Formula 11]

,

,

[Formula 12]

,

,

[Formula 13]

,

,

[Formula 14]

,

,

[Formula 15]

, 및

, and

[Formula 16]

In the above formula,

n is 1 to 200,

R ₁ and R ₂ are each independently a hydrogen atom, a halogen, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₂ to C ₁₀ alkenyl group, or a substituted or unsubstituted C ₂ to C ₁₀ alkyl Any one selected from a nyl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, and a substituted or unsubstituted C ₆ to C ₂₀ aryl group.

In one embodiment of the present invention, n may be 1 to 100, or 1 to 50.

The compounds of Formulas 5 to 16 may be, for example, compounds of Formulas 17 to 28 below:

[Formula 17]

,

,

[Formula 18]

,

,

[Formula 19]

,

,

[Formula 20]

,

,

[Formula 21]

,

,

[Formula 22]

,

,

[Formula 23]

,

,

[Formula 24]

,

,

[Formula 25]

,

,

[Formula 26]

,

,

[Formula 27]

, 및

, and

[Formula 28]

In the above formula,

n is 1 to 200;

In one embodiment of the present invention, n may be 1 to 100, or 1 to 50.

In an embodiment of the present invention, the oligomer having a repeating unit derived from the compound of Formula 1 may be used in an amount of 1 to 30 parts by weight, or 1 to 10 parts by weight based on 100 parts by weight of the hydroxyl group-containing polymer. When the content of the oligomer having a repeating unit derived from the compound of Formula 1 satisfies the above range, self-healing properties from tearing of the polyurethane film derived from the composition for forming a polyurethane film may be improved.

In the composition for forming a polyurethane film according to an embodiment of the present invention, the content of the hydroxyl group-containing polymer and the first isocyanate group-containing compound is, basically, a hydroxyl group in the hydroxyl group-containing polymer and Chemical Formula 1 The composition ratio can be determined in consideration of the stoichiometric reaction of a hydroxyl group that combines a hydroxyl group in an oligomer having a repeating unit derived from a compound of , and an isocyanate group included in the first isocyanate group-containing compound. According to the present invention, considering that a hydroxyl group is included in both the hydroxyl group-containing polymer and the oligomer having a repeating unit derived from the compound of Formula 1, the hydroxyl group-containing polymer and the first isocyanate group-containing compound content can be determined.

In addition, the degree of crosslinking of the hydroxyl group in the hydroxyl group-containing polymer and the hydroxyl group in the oligomer having a repeating unit derived from the compound of Formula 1 and the isocyanate group in the first isocyanate group-containing compound is the degree of crosslinking of the polyurethane film. It may be different depending on the purpose of use.

According to an embodiment of the present invention, the first isocyanate group-containing compound with respect to the number of hydroxyl groups in the oligomer having a hydroxyl group in the hydroxyl group-containing polymer and a repeating unit derived from the compound of Formula 1 plus the number of hydroxyl groups The ratio of the total number of isocyanate groups within (isocyanate group/hydroxyl group ratio) may be used in a ratio of 0.5 to 1.5, or 0.5 to 1, or 1 to 1.5, depending on the purpose of use. When the isocyanate group/hydroxyl group number ratio satisfies this range, mechanical properties, optical properties, and self-healing properties suitable for the purpose of use of the final film or coating material may be satisfied.

The composition for forming a polyurethane film according to the present invention includes a hydroxyl group-containing polymer; a first isocyanate group-containing compound; and an oligomer having a repeating unit derived from the compound of Formula 1, so that the urethane reaction is simultaneously performed between the hydroxyl group-containing polymer, the first isocyanate group-containing compound, and the oligomer having a repeating unit derived from the compound of Formula 1 can occur to form a polyurethane film.

In another aspect of the present invention, there is provided a polyurethane film derived from the composition for forming a polyurethane film.

Conventional polyurethane has a weak hydrogen bonding force between urethane, so it is difficult to show self-healing properties from tearing. However, in the polyurethane film derived from the composition for forming a polyurethane film of the present invention, the oxygen atom in the double ring of the compound of Formula 1 can form a strong hydrogen bond with the NH group of the urethane, so it can show self-healing properties from tearing. there is.

In addition, the film may have more improved mechanical properties, such as surface strength, than a polyurethane film derived from a composition including the compound of Formula 1 alone.

The polyurethane film is prepared by simultaneously stirring and mixing a hydroxyl group-containing polymer, a first isocyanate group-containing compound, and an oligomer having a repeating unit derived from the compound of Formula 1 to prepare a composition for forming a polyurethane film; and coating the composition for forming a polyurethane film on a substrate and drying the composition.

The composition for forming a polyurethane film may be obtained by mixing a hydroxyl group-containing polymer, a first isocyanate group-containing compound, an oligomer having a repeating unit derived from the compound of Formula 1, and a solvent, and the hydroxyl group-containing The polymer, the first isocyanate group-containing compound, and the oligomer having a repeating unit derived from the compound of Formula 1 are each mixed with a solvent in advance to prepare separate solutions, and then stirred and mixed together at room temperature (eg, 25 ° C.) may be obtained.

In the step of forming the composition for forming the polyurethane film, stirring and mixing may be performed for a short time, for example, 1 to 30 minutes, or 10 to 30 minutes, or 10 to 15 minutes.

The drying may be performed, for example, at 50 to 200° C. for 10 to 120 minutes, but is not limited thereto.

After preparing the composition for forming the polyurethane film, a step of degassing the composition for forming a polyurethane film between coating it on a substrate and drying the composition may be further included. The defoaming may be performed, for example, for 1 to 20 minutes, but is not limited thereto.

The reaction for forming the polyurethane film, that is, the urethane reaction, may proceed by reaction of a hydroxyl group contained in a side chain terminal of the hydroxyl group-containing polymer and an isocyanate group of the first isocyanate group-containing compound. At this time, as described above, the oligomer having a repeating unit derived from the compound of Formula 1 having a hydroxyl group may participate in the curing reaction together with the first isocyanate group-containing compound.

The composition includes known additives such as chain extenders, binding inhibitors, antistatic agents, antioxidants, biostabilizers, chemical molding agents, mold release agents, flame retardants, lubricants, colorants, flow improvers, fillers, lubricants, adhesion promoters, catalysts, Light stabilizers, optical brighteners, organic phosphorus compounds, oils, dyes, impact modifiers, reinforcing agents, strong fibers, weathering agents and plasticizers may be further included.

In addition, according to another aspect of the present invention, the substrate; And located on at least one surface of the substrate is provided an article comprising the above-described polyurethane film.

The substrate according to an embodiment of the present invention may be a metal substrate, a glass substrate, or a polymer substrate.

Specific examples of the articles may be transport devices such as automobiles, aircraft, ships, etc., and may be information and electronic products such as tablet PCs, displays, smartphones, wearable devices, defense security products, livestock products, building/industrial solvents, etc. They may be items of various fields.

Hereinafter, to help the understanding of the present invention, examples will be described in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the following examples. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

Example 1

(1) Preparation of an oligomer having a repeating unit derived from the compound of Formula 1

First, 8.58 g of solid child carbide was put into a three-neck flask, and 34.33 g of dimethylacetamide as a solvent was added, and then dissolved in a stirrer at 200 RPM for 10 minutes. Then, 4.29 g of hexamethylene diisocyanate was added, and finally, 0.064 g of dibutyltin dilaurate as a catalyst was added and reacted for 4 hours under oil base and nitrogen conditions at 70° C. to prepare an oligomer of Formula 17.

(2) Preparation of a composition for forming a polyurethane film

Styrene, butyl acrylate, 2-hydroxyethyl methacrylic acid, dodecyl methacrylate (mol% of 20 mol%, 30 mol%, 10 mol%, and 40 mol%, respectively) as a comonomer, and dimethylacet as a solvent The amides were mixed, but a comonomer solution was prepared so that the concentration of the total comonomer content was 50% by weight. Thereafter, 0.475 g of 2,2-azobisisobutyronitrile (AIBN) as an initiator was added to the comonomer solution, and radical polymerization was performed at 70° C. for 16 hours under reaction conditions for finally two or more hydroxyl groups. A polymer containing a hydroxyl group depending on the was prepared.

6 g of the prepared hydroxyl group-containing polymer and 0.09 g of the oligomer having a repeating unit derived from the prepared compound of Formula 1 were mixed by stirring at room temperature for 3 minutes using a paste mixer. Then, 0.63 g of hexamethylene diisocyanate, which is an isocyanate group-containing compound, was added, stirred at room temperature for 3 minutes using a paste mixer, and defoamed for 2 minutes to prepare a polyurethane film-forming composition. And at this time, the ratio of the number of isocyanate groups in the isocyanate group-containing compound to the number of hydroxyl groups in the oligomer having a hydroxyl group in the hydroxyl group-containing polymer and a repeating unit derived from the compound of Formula 1 to the number of hydroxyl groups (isocyanate) group/hydroxyl group number ratio) was 1.

3 ml of the polymer solution was applied to the prepared composition for forming a polyurethane film on a glass plate (7 x 5 cm ² ) and then coated using a wireless bar coater. A polyurethane film was prepared by placing the coated glass plate on a hot plate and drying it tertiarily at 70° C. for 30 minutes, 100° C. for 30 minutes, and 170° C. for 1 hour.

Example 2

A polyurethane film was prepared in the same manner as in Example 1, except that the oligomer of Chemical Formula 18 was prepared by adding methylene bis(4-cyclohexyl) diisocyanate instead of hexamethylene diisocyanate.

Example 3

A polyurethane film was prepared in the same manner as in Example 1, except that the oligomer of Chemical Formula 19 was prepared by adding naphthalene 1,5-diisocyanate instead of hexamethylene diisocyanate.

Example 4

A polyurethane film was prepared in the same manner as in Example 1, except that the oligomer of Chemical Formula 20 was prepared by adding diphenylmethane 4,4′-diisocyanate instead of hexamethylene diisocyanate.

Example 5

A polyurethane film was prepared in the same manner as in Example 1, except that the oligomer of Chemical Formula 21 was prepared by adding diphenylmethane 2,4′-diisocyanate instead of hexamethylene diisocyanate.

Example 6

A polyurethane film was prepared in the same manner as in Example 1, except that the oligomer of Chemical Formula 22 was prepared by adding diphenylmethane 2,2′-diisocyanate instead of hexamethylene diisocyanate.

Example 7

A polyurethane film was prepared in the same manner as in Example 1, except that the oligomer of Chemical Formula 23 was prepared by adding m-xylene diisocyanate instead of hexamethylene diisocyanate.

Example 8

A polyurethane film was prepared in the same manner as in Example 1, except that the oligomer of Chemical Formula 24 was prepared by adding isophorone diisocyanate instead of hexamethylene diisocyanate.

Example 9

A polyurethane film was prepared in the same manner as in Example 1, except that the oligomer of Chemical Formula 25 was prepared by adding trans-1,4-cyclohexane diisocyanate instead of hexamethylene diisocyanate.

Example 10

A polyurethane film was prepared in the same manner as in Example 1, except that the oligomer of Chemical Formula 26 was prepared by adding 2,4,4-trimethyl hexamethylene diisocyanate instead of hexamethylene diisocyanate.

Example 11

A polyurethane film was prepared in the same manner as in Example 1, except that the oligomer of Chemical Formula 27 was prepared by adding tolylene 2,4-diisocyanate instead of hexamethylene diisocyanate.

Example 12

A polyurethane film was prepared in the same manner as in Example 1, except that the oligomer of Chemical Formula 28 was prepared by adding phenylene 1,4-diisocyanate instead of hexamethylene diisocyanate.

Comparative Example 1

A composition for forming a polyurethane film was prepared in the same manner as in Example 1 except that the oligomer having a repeating unit derived from the compound of Formula 1 was not included, and a polyurethane film coated on the substrate was prepared.

Comparative Example 2

A composition for forming a polyurethane film was prepared in the same manner as in Example 1, except that child carbide was used alone instead of an oligomer having a repeating unit derived from the compound of Formula 1, and a polyurethane film coated on a substrate was prepared. prepared.

Evaluation Example 1:

self-healing properties

For the polyurethane films finally obtained in Example 1 and Comparative Example 1, after stimulation with an iso-tip of 3N hardness, the self-healing process was photographed by placing it at a temperature 10° C. higher than the respective glass transition temperature. was taken, and the results are shown in FIGS. 1 and 2 , respectively.

As confirmed in Figure 1, the polyurethane film of Example 1 is self-healing, while as confirmed in Figure 2, it can be confirmed that the polyurethane film of Comparative Example 1 did not self-healing at all. .

That is, the polyurethane film derived from the composition for forming a polyurethane film according to the present invention can be restored to the same level as the initial surface state by self-healing within a very short time.

Evaluation Example 2:

Surface strength evaluation

For the polyurethane film finally obtained in Example 1 and Comparative Example 2, after applying a load of 1N using a single scratch tester, the surface of the polyurethane film was photographed, and the results are shown in FIGS. 3 and 4 Each is shown.

As can be seen in Figure 3, the polyurethane film obtained in Example 1 did not change the surface even after applying a load of 1N.

On the other hand, as confirmed in FIG. 4, it was confirmed that the polyurethane film obtained in Comparative Example 2 had a tearing phenomenon on the surface after applying a load of 1N.

That is, the polyurethane film derived from the composition for forming a polyurethane film according to the present invention may have improved surface strength than the polyurethane film derived from the composition for forming a polyurethane film including the child carbide compound alone.

Claims (14)

a hydroxyl group-containing polymer; a first isocyanate group-containing compound; And a composition for forming a polyurethane film comprising a compound of formula (3):
[Formula 3]

In the above formula,
n is 1 to 200,
R ₁ and R ₂ are each independently a hydrogen atom, a halogen, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₂ to C ₁₀ alkenyl group, or a substituted or unsubstituted C ₂ to C ₁₀ alkyl Any one selected from the group consisting of a nyl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, and a substituted or unsubstituted C ₆ to C ₂₀ aryl group,
R is a substituted or unsubstituted C ₁ to C ₁₀ alkylene group, a substituted or unsubstituted C ₂ to C ₁₀ alkenylene group, a substituted or unsubstituted C ₂ to C ₁₀ alkynylene group, a substituted or unsubstituted C ₃ To C ₃₀ cycloalkylene group, a substituted or unsubstituted C ₃ to C ₃₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ to C ₃₀ arylene group, and a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group Any one selected from the group consisting of or a divalent linking group to which two or more of them are bonded. delete delete According to claim 1,
The compound of Formula 3 is a composition for forming a polyurethane film, characterized in that it is a compound of Formula 4:
[Formula 4]

In the above formula,
n is 1 to 200,
R is a substituted or unsubstituted C ₁ to C ₁₀ alkylene group, a substituted or unsubstituted C ₂ to C ₁₀ alkenylene group, a substituted or unsubstituted C ₂ to C ₁₀ alkynylene group, a substituted or unsubstituted C ₃ To C ₃₀ cycloalkylene group, a substituted or unsubstituted C ₃ to C ₃₀ heterocycloalkylene group, a substituted or unsubstituted C ₆ to C ₃₀ arylene group, and a substituted or unsubstituted C ₅ to C ₃₀ heteroarylene group Any one selected from the group consisting of or a divalent linking group to which two or more of them are bonded. According to claim 1,
R is a substituted or unsubstituted, methylene group, ethylene group, propylene group, isopropylene group, butylene group, sec-butylene group, t-butylene group, n-butylene group, pentylene group, hexylene group, cyclopropylene group , cyclobutylene group, cyclopentylene group, cyclohexylene group, dicyclohexylenemethane group, isophoronylene group, phenylene group, benzylene group, diphenylenemethane group, diphenyleneethane group, xylene group, A composition for forming a polyurethane film, characterized in that it is any one selected from the group consisting of a tolylene group and a naphthalene group. According to claim 1,
The compound of Formula 3 is a composition for forming a polyurethane film, characterized in that any one of the compounds of Formulas 5 to 16:
[Formula 5]

,
[Formula 6]

,
[Formula 7]

,
[Formula 8]

,
[Formula 9]

,
[Formula 10]

,
[Formula 11]

,
[Formula 12]

,
[Formula 13]

,
[Formula 14]

,
[Formula 15]

, and
[Formula 16]

In the above formula,
n is 1 to 200,
R ₁ and R ₂ are each independently a hydrogen atom, halogen, a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, a substituted or unsubstituted C ₂ to C ₁₀ alkenyl group, or a substituted or unsubstituted C ₂ to C ₁₀ alkyl Any one selected from a nyl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, and a substituted or unsubstituted C ₆ to C ₂₀ aryl group. 7. The method of claim 6,
The compound of Formula 3 is a composition for forming a polyurethane film, characterized in that any one of the compounds of Formulas 17 to 28:
[Formula 17]

[Formula 18]

,
[Formula 19]

,
[Formula 20]

,
[Formula 21]

,
[Formula 22]

,
[Formula 23]

,
[Formula 24]

,
[Formula 25]

,
[Formula 26]

,
[Formula 27]

, and
[Formula 28]

In the above formula,
n is 1 to 200; The method of claim 1,
The hydroxyl group-containing polymer is a hydroxyl group-containing polyacrylate-based compound; a hydroxyl group-containing polymethacrylate-based compound; hydroxyl group-containing polystyrene-based compounds; a polymer including a repeating unit derived from two or more monomers selected from a hydroxyl group-containing acrylate-based monomer, a hydroxyl group-containing methacrylate-based monomer, and a hydroxyl group-containing styrene-based monomer; Or a composition for forming a polyurethane film comprising two or more of them. The method of claim 1,
The compound of Formula 3 is a composition for forming a polyurethane film, characterized in that it is included in an amount of 1 to 30 parts by weight based on 100 parts by weight of the hydroxyl group-containing polymer. The method of claim 1,
The composition for forming a polyurethane film, characterized in that the hydroxyl group-containing polymer has a number average molecular weight in the range of 100 to 1,000,000. The method of claim 1,
The ratio of the total number of isocyanate groups in the isocyanate group-containing compound to the total number of hydroxyl groups that are the sum of the hydroxyl groups in the hydroxyl group-containing polymer and the hydroxyl groups in the compound of Formula 3 (isocyanate groups/hydroxyl group number ratio) is A composition for forming a polyurethane film, characterized in that 0.5 to 1.5. 12. A polyurethane film derived from the composition for forming a polyurethane film according to any one of claims 1 and 4 to 11. Board; and
An article positioned on at least one surface of the substrate and comprising the polyurethane film according to claim 12 . 14. The method of claim 13,
wherein the substrate is a metal substrate, a glass substrate, or a polymer substrate.

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