KR20210010028A - Monomer compound for carbamic acid derivative polymer, carbamic acid derivative polymer, polymer resin composition, polymer film and auromobile part comprising the same - Google Patents

Abstract

The present invention relates to a monomer compound for synthesizing a carbamic acid derivative polymer having a specific structure, to a carbamic acid derivative polymer, to a polymer film comprising the same, and to automotive parts comprising the same. The monomer compound has excellent UV protection and optical properties.

Description

Monomer compound for carbamic acid derivative polymer synthesis, carbamic acid derivative polymer, polymer resin composition, polymer film, and automotive parts containing the same. COMPRISING THE SAME}

The present invention relates to a monomer compound for synthesizing a carbamic acid derivative polymer, a carbamic acid derivative polymer, a polymer resin composition, a polymer film, and automobile parts including the same.

Since carbamic acid derivative polymers such as polyurethane and polyurea are relatively inexpensive, easy to mold, and have high elasticity, they are mainly used in automobile fields and clothing fields.

In particular, films using a carbamic acid derivative polymer are used in automobile parts and engineering parts. For example, a polyurethane film having a high-gloss surface can be used to protect the painted surface of an automobile, and thus, a polyurethane film that has a gloss above a level that does not degrade the gloss of the painted surface and at the same time has UV-blocking ability. Film is in demand.

In order to overcome this, a polyurethane film with a sunscreen added as an additive was used, but the compatibility between the sunscreen and the polyurethane resin was poor, so agglomeration occurred in the finished product, resulting in a decrease in the sunscreen ability. There was a problem in that the blocking ability was realized only for ultraviolet rays within the wavelength range.

Accordingly, there is a need for development of a polyurethane film that has excellent durability and can realize excellent UV blocking ability in a wide wavelength range of the UV region.

An object of the present invention is to provide a monomer compound for synthesizing a carbamic acid derivative polymer capable of realizing excellent UV blocking ability and optical properties, as well as high reliability and durability.

In addition, the present invention is to provide a carbamic acid derivative polymer comprising the monomer compound for synthesizing the carbamic acid derivative polymer as a monomer.

In addition, the present invention is to provide a polymer resin composition comprising the carbamic acid derivative polymer.

In addition, the present invention is to provide a polymer film comprising a cured product of the polymer resin composition.

In addition, the present invention is to provide a component for a vehicle using the polymer film.

In the present specification, a monomer for synthesizing a carbamic acid derivative polymer represented by the following Chemical Formula 1 is provided.

[Formula 1]

In Formula 1, D ₁ is -OH or -NH ₂ , T ₁ is a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO ₂ -, -CONH- , -N(R ₁ )-, -P(R ₂ )-, and R ₁ and R ₂ is each independently hydrogen or one of a hydrocarbon-based monovalent functional group having 1 to 10 carbon atoms, L ₁ is a hydrocarbon-based divalent functional group having 3 to 10 carbon atoms, and Y is a monovalent functional group containing a conjugate structure And n is an integer of 2 to 5.

In the present specification, a carbamic acid derivative polymer including a first repeating unit represented by the following Chemical Formula 3 is provided.

[Chemical Formula 3]

In Formula 3, X ₁ and X ₂ are each independently -O- or -NH-, and L _4, L _5, L ₆ and L'are each independently a hydrocarbon-based divalent functional group having 3 or more and 10 or less carbon atoms. , T ₄ , T ₅ and T'is each independently a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO ₂ -, -CONH-, -N(R ₉ )-, -P(R ₁₀ )- is any one of, and R ₉ and R ₁₀ is each independently hydrogen or one of a hydrocarbon-based monovalent functional group having 1 to 10 carbon atoms, D'is -OH or -NH ₂ , Y ₁ is a monovalent functional group containing a conjugate structure, n 'Is an integer from 0 to 3.

In the present specification, there is also provided a polymer resin composition comprising the carbamic acid derivative polymer.

In the present specification, a polymer film including a cured product of the polymer resin composition is provided.

In the present specification, a component for automobiles including the polymer film is also provided.

Hereinafter, a monomer compound for synthesizing a carbamic acid derivative polymer, a carbamic acid derivative polymer, a polymer resin composition, a polymer film, and automobile parts including the same according to a specific embodiment of the present invention will be described in more detail.

Unless expressly stated in the specification, terminology is only intended to refer to specific embodiments and is not intended to limit the invention.

The singular forms used in the present specification also include plural forms unless the phrases clearly indicate the opposite.

The meaning of'comprising' as used herein specifies a specific characteristic, region, integer, step, action, element and/or component, and other specific characteristic, region, integer, step, action, element, component and/or group It does not exclude the existence or addition of

Further, in the present specification, terms including ordinal numbers such as'first' and'second' are used for the purpose of distinguishing one component from other components, and are not limited by the ordinal number. For example, within the scope of the present invention, a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element.

In the present specification, the weight average molecular weight was measured using an Agilent PL gel mixed-B column using an Agilent 1260 Infinity II instrument, the evaluation temperature was 40 °C, and Tetrahydrofuran was used as a solvent, and the flow rate was 1.0 mL/min. The sample was prepared at a concentration of 1 mg/10 mL, and then supplied in an amount of 100 μL, and the value of Mw was calculated using a calibration curve formed using a polystyrene standard. The molecular weight of the polystyrene standards was 580 / 1,300 / 4,880 / 9,570 / 17,970 / 67,600 / 206,000 / 466,300 / 1,044,000 / 3,152,000 / 6,570,000.

In the present specification, the term "substitution" means that other functional groups are bonded in place of a hydrogen atom in the compound, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same or different from each other.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amide group; Primary amino group; Carboxyl group; Sulfonic acid group; Sulfonamide group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkoxysilylalkyl group; Arylphosphine group; Or it means a substituted or unsubstituted substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O and S atoms, or linked with two or more substituents among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, a multivalent functional group is a residue in which a plurality of hydrogen atoms bonded to an arbitrary compound has been removed, and examples thereof include a divalent functional group, a trivalent functional group, and a tetravalent functional group. For example, a tetravalent functional group derived from cyclobutane refers to a residue in the form of removal of any 4 hydrogen atoms bonded to cyclobutane.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine, or iodine.

In the present specification, hydrocarbon may mean an organic compound consisting of only carbon and hydrogen. For example, it may mean a compound such as alkanes, alkenes, and arenes.

In the present specification, the alkyl group is a monovalent functional group derived from alkane and may be linear or branched, and the number of carbon atoms of the linear alkyl group is not particularly limited, but is preferably 1 to 20. Further, the branched chain alkyl group has 3 to 20 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl- Propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl, and the like, but are not limited thereto. The alkyl group may be substituted or unsubstituted.

In the present specification, the haloalkyl group refers to a functional group in which a halogen group is substituted with the above-described alkyl group, and examples of the halogen group include fluorine, chlorine, bromine, or iodine. The haloalkyl group may be substituted or unsubstituted.

In the present specification, the aryl group is a monovalent functional group derived from arene, and may be a monocyclic aryl group or a polycyclic aryl group. The monocyclic aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto. The aryl group may be substituted or unsubstituted.

In the present specification, the arylene group is a divalent functional group derived from arene, and the description of the aryl group described above may be applied except that these are divalent functional groups.

, 또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

, or

Means a bond connected to another substituent.

In the present specification, a direct bond or a single bond means that no atom or group of atoms exists at the corresponding position and is connected by a bonding line.

In the present specification, the conjugate structure means a structure including conjugation and may mean a conjugated structure. Specifically, it may mean a state in which three or more p orbitals of neighboring elements are continuously overlapped.For example, in the case of a compound in which a double bond and a single bond are located on a plane, and a double bond and a single bond alternate, conjugate It can be a structure.

In the present specification, the carbamic acid derivative may mean a compound derived from carbamic acid, and may be, for example, a carbamic acid imide or a carbamic acid ester.

In the present specification, the carbamic acid derivative polymer refers to a polymer prepared by polymerizing the carbamic acid derivative as a monomer, and specifically, may mean a polyurethane (co)polymer or a polyurea (co)polymer.

In the present specification, the (co)polymer means including all polymers or copolymers, the polymer means a homopolymer consisting of a single repeating unit, and the copolymer means a composite polymer containing two or more repeating units.

In the present specification, (co)polymer is used in the sense of including all of a random (co) polymer, a block (co) polymer, and a graft (co) polymer.

Ⅰ. Monomer compound for synthesis of carbamic acid derivative polymer

According to an embodiment of the present invention, a monomer compound for synthesizing a carbamic acid derivative polymer represented by Chemical Formula 1 may be provided.

The present inventors have conducted research on components that can be used in automobile parts, and, like the monomer compound for synthesizing the carbamic acid derivative polymer of the above embodiment, when the compound of Formula 1 is included, it has excellent UV blocking ability even at a long wavelength. At the same time, it was confirmed through an experiment that excellent optical properties could be realized and the invention was completed.

Specifically, in the case of a sunscreen that was conventionally applied in the form of an additive to the carbamic acid derivative polymer composition, as it is post-added in the form of an additive, the compatibility with the carbamic acid derivative polymer is poor, so that not only agglomeration phenomenon occurs in the composition, but also manufactured therefrom. Agglomeration occurs even in the polymer film, which has a technical problem that not only decreases the UV blocking ability, but also results in poor durability of the product.

In contrast, in the case of the compound of Formula 1 according to an embodiment of the present invention, since it can directly act as a monomer for synthesizing a carbamic acid derivative, there is no problem of compatibility with the polymer resin, and there is room for agglomeration phenomenon. It was confirmed that the durability of the product can also be improved while realizing remarkably excellent UV blocking ability because there is no absence.

In addition, in the case of a polymer film including a UV blocker applied in the form of a conventional additive, there is a problem in that the blocking ability is significantly deteriorated in the case of UV having a wavelength of 400 nm or more while blocking UV having a wavelength of 200 nm to 400 nm.

In contrast, in the case of the polymer film including the compound of Formula 1 according to an embodiment of the present invention, excellent ultraviolet ray blocking ability is realized even for ultraviolet rays in the range of 400 nm or more and 420 nm or less, regardless of the wavelength range. It was confirmed that blocking ability can be implemented.

More specifically, as represented by Y in Chemical Formula 1, as the monovalent functional group containing the conjugate structure is substituted on the benzene ring, it is possible to control the maximum absorption wavelength of the sunscreen, and the urethane prepared by copolymerizing it It was confirmed that the technical effect of controlling the UV blocking performance of the film was implemented. In particular, when Y in Formula 1 is substituted with a cyano group, the maximum absorption wavelength of the sunscreen agent has shifted to a long wavelength, and the urethane film containing a sunscreen agent in which Y in Formula 1 is substituted with a cyano group is blocked at a long wavelength. It was confirmed that the ability was excellent.

In addition, as L ₁ in the general formula (1), isocyanate-based compound reacts with the carboxylic acid functional group is -OH or -NH ₂ can make a derivative polymer having the carbon number of 3 or more 10 hydrocarbon-based divalent benzene ring to a group with the following parameters By binding to, the solubility of the monomer compound for synthesizing the carbamic acid derivative polymer increases, so that the reliability of the polymer film prepared therefrom may be improved.

Looking at the monomer compound for synthesizing the carbamic acid derivative polymer of the embodiment in more detail, in Formula 1, D ₁ may be -OH or -NH ₂ . When D _{1 is} OH or -NH ₂ , a carbamic acid derivative polymer may be synthesized by reacting with an isocyanate compound. Specifically, when D ₁ is -OH, it may be a monomer of polyurethane, and when D ₁ is -NH ₂ , it may be a monomer of polyurea.

In Formula 1, T ₁ is a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO ₂ -, -CONH-, -N(R ₁ )-, -P (R ₂ )- is any one of, and R ₁ and Each of R ₂ may independently be one of hydrogen or a hydrocarbon-based monovalent functional group having 1 to 10 carbon atoms. Specifically, T ₁ may be -O-.

In Formula 1, L ₁ may be a hydrocarbon-based divalent functional group having 3 or more and 10 or less carbon atoms. As L ₁ is a hydrocarbon-based divalent functional group having 3 or more and 10 or less carbon atoms, the solubility of the monomer compound for synthesizing the carbamic acid derivative polymer represented by Formula 1 increases as described above, and the reliability of the polymer film produced therefrom Can be improved. The hydrocarbon-based divalent functional group having 3 or more and 10 or less carbon atoms is not greatly limited, but an alkylene group having 3 or more and 10 or less carbon atoms, a cycloalkylene group having 3 or more and 10 or less carbon atoms, an alkenylene group having 3 or more and 10 or less carbon atoms, or 3 or more carbon atoms It may be one of 10 or less arylene groups. For example, in Formula 1, L ₁ may be an alkylene group having 3 or more and 10 or less carbon atoms, an alkylene group having 5 or more and 10 or less carbon atoms, and more specifically, a hexylene group.

In Formula 1, Y may be a monovalent functional group containing a conjugate structure. As Y is a monovalent functional group containing a conjugate structure, it is possible to adjust the maximum absorption wavelength of the sunscreen as described above, and thus an effect of excellently blocking ultraviolet rays of a long wavelength can be realized.

Specifically, the monovalent functional group containing the conjugate structure may be represented by the following formula (2).

[Formula 2]

In Formula 2, A ₁ is _one of hydrogen or a hydrocarbon-based monovalent functional group, A ₂ and A ₃ is each independently a cyano group, one of -(C=O)-NR ₄ R ₅ or -(C=O)-OR ₆ , and R _4, R ₅ and Each of R ₆ is independently hydrogen or one of an alkyl group having 1 or more and 10 or less carbon atoms, an alkenyl group having 2 or more and 10 or less carbon atoms, or an alkynyl group having 2 or more and 10 or less carbon atoms. R _4, R ₅ and R ₆ may each independently be an alkyl group having 1 or more and 10 or less carbon atoms, or an alkyl group having 2 or more and 5 or less carbon atoms, and may be, for example, an ethyl group.

That is, A ₂ and Each of A ₃ may independently be a cyano group or an ester group.

Specifically, in Chemical Formula 2, A ₁ may be specifically hydrogen.

In addition, A ₂ and At least one of A ₃ may be a cyano group, and the remainder may be -(C=O)-OR ₆ . That is, A ₂ and At least one of A ₃ may be a cyano group and the rest may be an ester group.

According to an embodiment of the present invention, in Formula 1, n is an integer of 2 to 5.

Specifically, in Formula 1, n may be 2, and accordingly, two -OH or -NH ₂ may be substituted on the benzene ring. That is, the monomer compound for synthesizing the carbamic acid derivative polymer represented by Formula 1 may be a diol compound or a diamine compound.

According to an embodiment of the present invention, the monomer compound for synthesizing the carbamic acid derivative polymer may be represented by the following Formula 1-1.

[Formula 1-1]

In Formula 1-1, D ₂ and D ₃ are each independently -OH or -NH ₂ , and T ₂ and T ₃ are each independently a single bond, -O-, -CO-, -COO-, -S -, -SO-, -SO ₂ -, -CONH-, -N(R ₁ )-, -P(R ₂ )-, and R ₁ and R ₂ is each independently hydrogen or one of a hydrocarbon-based monovalent functional group having 1 or more and 10 or less carbon atoms, L ₂ and L ₃ are each independently a hydrocarbon-based divalent functional group having 3 or more and 10 or less carbon atoms, and Y is a conjugate structure It is a monovalent functional group containing

As the two -OH or -NH ₂ are each substituted at the meta position of the benzene ring as in Formula 1-1, The stereoscopic rush of the carbamic acid derivative polymer synthesized by the monomer compound for synthesizing the carbamic acid derivative polymer may be reduced.

More specifically, the monomer compound for synthesizing the carbamic acid derivative polymer may be one of the compounds represented by the following Chemical Formulas 1-2 to 1-3.

[Formula 1-2]

[Formula 1-3]

.

.

Ⅱ. Carbamic acid derivative polymer

According to another embodiment of the present invention, a carbamic acid derivative polymer including a first repeating unit represented by Chemical Formula 3 is provided.

The first repeating unit represented by Formula 3 may be a repeating unit derived from the above-described monomer compound for synthesizing a carbamic acid derivative polymer.

In Formula 3, X ₁ and X ₂ may each independently be -O- or -NH-. Since X ₁ and X ₂ are each independently -O- or -NH-, the carbamic acid derivative polymer according to an embodiment of the present invention may be polyurethane or polyurea. Specifically, when X ₁ and X ₂ are -O-, the carbamic acid derivative polymer may be a polyurethane, and when X ₁ and X ₂ are -NH-, the carbamic acid derivative polymer may be polyurethane.

In Formula 3, T ₄ , T ₅ and T'is each independently a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO ₂ -, -CONH-, -N(R ₉ )-, -P(R ₁₀ )- is any one of, and R ₉ and R ₁₀ may each independently be hydrogen or a hydrocarbon monovalent functional group having 1 to 10 carbon atoms. Specifically, T ₄ , T ₅ and T'may be -O-.

In Formula 3, L _4, L _5, L ₆ and L′ may each independently be a hydrocarbon-based divalent functional group having 3 or more and 10 or less carbon atoms. As L _4, L _5, L ₆ and L′ are hydrocarbon-based divalent functional groups having 3 or more and 10 or less carbon atoms, reliability of a polymer film prepared from a carbamic acid derivative polymer may be improved.

In Formula 3, L ₄ may be a divalent functional group derived from a polyfunctional isocyanate compound.

The polyfunctional isocyanate compound may include at least one of an aromatic polyfunctional isocyanate compound, an alicyclic polyfunctional isocyanate compound, and an aliphatic polyfunctional isocyanate compound.

Specifically, the aromatic polyfunctional isocyanate compound is 2,4-tolylene diisocyanate (TDI: tolylene diisocyanate), 2,6-tolylene diisocyanate (TDI: tolylene diisocyanate), m-phenylene diisocyanate, p-phenylene diisocyanate , 4,4'-diphenylmethane diisocyanate (MDI: Methylene diphenyl diisocyanate), 2,4'-diphenylmethane diisocyanate (MDI: Methylene diphenyl diisocyanate), 2,2'-diphenylmethane diisocyanate (MDI: Methylene diphenyl diisocyanate), xylylene diisocyanate (XDI), 3,3'-dimethyl-4,4'-biphenylenediisocyanate, and 3,3'-dimethoxy-4,4'-biphenylenedi It may include at least one of isocyanates.

In addition, the alicyclic polyfunctional isocyanate compound is 4,4'-methylene dicyclohexyl diisocyanate (H12-MDI: 4,4'-Methylene dicyclohexyl diisocyanate), cyclohexane-1,4-diisocyanate, isophorone Diisocyanate (IPDI: isophorone diisocyanate), dicyclohexylmethane-4,4'-diisocyanate, and hydrated xylylene diisocyanate (H6-XDI: Hydrogenated xylylene diisocyanate), and methylcyclohexane diisocyanate. I can.

In addition, the aliphatic polyfunctional isocyanate compound may include at least one of butane-1,4-diisocyanate, hexamethylene diisocyanate (HDI), isopropylene diisocyanate, methylene diisocyanate, and lysine isocyanate. .

In Formula 3, L _5, L ₆ and L′ may be a hydrocarbon-based divalent functional group having 3 or more and 10 or less carbon atoms derived from the monomer compound for synthesizing the carbamic acid derivative polymer of the above-described embodiment.

In Formula 3, L _5, L ₆ and L'are not greatly limited, but an alkylene group having 3 or more and 10 or less carbon atoms, a cycloalkylene group having 3 or more and 10 or less carbon atoms, an alkenylene group having 3 or more and 10 or less carbon atoms, or It may be one of 3 or more and 10 or less arylene groups. For example, in Formula 3, L _5, L ₆ and L′ may be an alkylene group having 3 or more and 10 or less carbon atoms, an alkylene group having 5 or more and 10 or less carbon atoms, and more specifically, a hexylene group.

In Formula 3, Y ₁ may be a monovalent functional group containing a conjugate structure. As Y ₁ is a monovalent functional group containing a conjugate structure, it is possible to adjust the maximum absorption wavelength of the sunscreen agent as described above, and thus an effect of excellently blocking ultraviolet rays of a long wavelength can be realized.

Specifically, the monovalent functional group containing the conjugate structure may be represented by the following formula (2).

[Formula 2]

In Formula 2, A ₁ is _one of hydrogen or a hydrocarbon-based monovalent functional group, A ₂ and A ₃ is each independently a cyano group, one of -(C=O)-NR ₄ R ₅ or -(C=O)-OR ₆ , and R _4, R ₅ and Each of R ₆ is independently one of an alkyl group having 1 or more and 10 or less carbon atoms, an alkenylene group having 2 or more and 10 or less carbon atoms, and an alkynylene group having 2 or more and 10 or less carbon atoms. R _4, R ₅ and R ₆ may each independently be an alkyl group having 1 or more and 10 or less carbon atoms, or an alkyl group having 2 or more and 5 or less carbon atoms, and may be, for example, an ethyl group.

That is, A ₂ and Each of A ₃ may independently be a cyano group or an ester group.

Specifically, in Chemical Formula 2, A ₁ may be specifically hydrogen.

In addition, A ₂ and At least one of A ₃ may be a cyano group, and the remainder may be -(C=O)-OR ₆ . That is, A ₂ and At least one of A ₃ may be a cyano group and the rest may be an ester group.

According to an embodiment of the present invention, in Chemical Formula 3, n'is an integer of 0 to 3.

Specifically, in Chemical Formula 3, n'may be 0.

Carbamic acid derivative polymer according to an embodiment of the present invention is a second repeating unit represented by the following formula (4); Alternatively, a third repeating unit represented by the following Chemical Formula 5 may be further included.

[Formula 4]

[Formula 5]

In Formulas 4 and 5, X ₃ to X ₆ are each independently -O- or -NH-, L ₇ to L ₁₁ are each independently a hydrocarbon-based divalent functional group having 1 or more and 20 or less carbon atoms, and m is It is an integer greater than or equal to 1.

Specifically, the second repeating unit may be a repeating unit derived from a reaction of a chain extender and a polyfunctional isocyanate compound, and the third repeating unit is a repeating unit derived from a reaction of a polycarbonate diol and a polyfunctional isocyanate compound. It can be a unit.

That is, the carbamic acid derivative polymer of the embodiment may include a soft segment and a hard segment, and the soft segment is a third repetition derived from the polycarbonate diol and a polyfunctional isocyanate compound. A unit may be included, and the hard segment may include a second repeating unit derived from the chain extender and a polyfunctional isocyanate compound.

In Formulas 4 and 5, L ₇ and L ₉ may be a hydrocarbon-based divalent functional group derived from a polyfunctional isocyanate-based compound.

The polyfunctional isocyanate compound may include at least one of an aromatic polyfunctional isocyanate compound, an alicyclic polyfunctional isocyanate compound, and an aliphatic polyfunctional isocyanate compound.

Specifically, the aromatic polyfunctional isocyanate compound is 2,4-tolylene diisocyanate (TDI: tolylene diisocyanate), 2,6-tolylene diisocyanate (TDI: tolylene diisocyanate), m-phenylene diisocyanate, p-phenylene diisocyanate , 4,4'-diphenylmethane diisocyanate (MDI: Methylene diphenyl diisocyanate), 2,4'-diphenylmethane diisocyanate (MDI: Methylene diphenyl diisocyanate), 2,2'-diphenylmethane diisocyanate (MDI: Methylene diphenyl diisocyanate), xylylene diisocyanate (XDI), 3,3'-dimethyl-4,4'-biphenylenediisocyanate, and 3,3'-dimethoxy-4,4'-biphenylenedi It may include at least one of isocyanates.

In addition, the alicyclic polyfunctional isocyanate compound is 4,4'-methylene dicyclohexyl diisocyanate (H12-MDI: 4,4'-Methylene dicyclohexyl diisocyanate), cyclohexane-1,4-diisocyanate, isophorone Diisocyanate (IPDI: isophorone diisocyanate), dicyclohexylmethane-4,4'-diisocyanate, and hydrated xylylene diisocyanate (H6-XDI: Hydrogenated xylylene diisocyanate), and methylcyclohexane diisocyanate. I can.

In addition, the aliphatic polyfunctional isocyanate compound may include at least one of butane-1,4-diisocyanate, hexamethylene diisocyanate (HDI), isopropylene diisocyanate, methylene diisocyanate, and lysine isocyanate. .

In addition, in Formula 4, L ₈ may be a hydrocarbon-based divalent functional group derived from a chain extender.

The chain extender may include a diol having 1 or more and 10 or less carbon atoms, or a diol having 4 or more and 6 or less carbon atoms. The chain extender containing a diol having a carbon number in the above-described range can effectively extend the chain of the polyfunctional isocyanate compound. Specifically, the chain extender is 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, opentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol and 1, It may contain at least one of 4-cyclohexanedimethanol.

That is, in Chemical Formula 4, L ₈ is not particularly limited, but an alkylene group having 1 or more and 10 or less carbon atoms, a cycloalkylene group having 1 or more and 10 or less carbon atoms, an alkenylene group having 1 or more and 10 or less carbon atoms, or 1 or more and 10 or less carbon atoms. It may be one of the arylene groups. For example, in Formula 4, L ₈ may be an alkylene group having 1 or more and 10 or less carbon atoms, and more specifically, may be a butylene group.

In addition, in Formula 5, L ₁₀ and L ₁₁ may be a hydrocarbon-based divalent functional group derived from a polycarbonate diol.

In one embodiment of the invention, the number of carbon atoms constituting the diol used as the chain extender may be smaller than the number of carbon atoms constituting the polycarbonate diol. In this case, as the chain extender has a higher fluidity than the polycarbonate diol, the reaction between the polyfunctional isocyanate compound and the chain extender may occur before the reaction of the polycarbonate diol and the polyfunctional isocyanate compound. Specifically, when butanediol is used as a chain extender, one hydroxy group of two hydroxy groups of butanediol reacts with and bonds with the isocyanate group of the polyfunctional isocyanate compound, and the unreacted hydroxy group of the butanediol is polyfunctional. As the process of bonding with the new isocyanate group of the isocyanate-based compound is repeated, a second polyfunctional isocyanate-based compound having a new structure having an elongated chain structure may be formed. Thereafter, the second polyfunctional isocyanate-based compound having an elongated chain structure and the polycarbonate diol may react with each other to form the carbamic acid derivative polymer of the embodiment described above.

That is, the carbamic acid derivative polymer of the above-described embodiment may be prepared by reaction of the monomer compound for synthesizing the carbamic acid derivative polymer of the above-described embodiment, a chain extender, a polycarbonate diol, and a polyfunctional isocyanate-based compound.

In the carbamic acid derivative polymer according to an embodiment of the present invention, the first repeating unit is 0.1 mol% or more and 10 mol% or less, 0.1 mol% or more and 8 mol% or less, 0.1 mol% or more with respect to the total repeating units of the carbamic acid derivative polymer. 5 mol% or less, or 0.1 mol% or more and 2 mol% or less.

Alternatively, the carbamic acid derivative polymer according to an embodiment of the present invention contains 0.1 mol% or more of the monomer compound for synthesizing the carbamic acid derivative polymer based on the total number of moles of the monomer compound for synthesizing the carbamic acid derivative polymer, the chain extender, and the polycarbonate diol. A monomer compound for synthesizing a carbamic acid derivative polymer containing 10 mol% or less, 0.1 mol% or more and 8 mol% or less, 0.1 mol% or more and 5 mol% or less, or 0.1 mol% or more and 2 mol% or less, a chain extender, and poly It can be prepared by reaction of a carbonate diol.

When the first repeating unit is contained in an amount of less than 0.1 mol% with respect to the total repeating units of the carbamic acid derivative polymer, the UV blocking ability of the polymer film prepared from the carbamic acid derivative polymer may not be sufficiently implemented. When the first repeating unit is contained in an amount exceeding 10 mol% with respect to the total repeating unit, a technical problem may occur in that mechanical properties of a polymer film prepared from a carbamic acid derivative polymer are deteriorated or reliability is lowered.

In addition, in the carbamic acid derivative polymer according to an embodiment of the present invention, the second repeating unit is 50 mol% or more and 85 mol% or less, 50 mol% or more and 80 mol% or less, 50 mol% with respect to the total repeating units of the carbamic acid derivative polymer. It may be included in an amount of not less than 70 mol% or not less than 55 mol% and not more than 65 mol%, and the third repeating unit is 10 mol% or more and 40 mol% or less, 20 mol% or more 40 mol with respect to the total repeating units of the carbamic acid derivative polymer. % Or less, 30 mol% or more and 40 mol% or less, or 35 mol% or more and 40 mol% or less.

Alternatively, the carbamic acid derivative polymer according to an embodiment of the present invention contains 50 mol% or more and 85 mol% or less of the chain extender based on the total number of moles of the monomer compound for synthesizing the carbamic acid derivative polymer, the chain extender, and the polycarbonate diol, 50 mol% or more and 80 mol% or less, 50 mol% or more and 70 mol% or less, or 55 mol% or more and 65 mol% or less, and polycarbonate diols 10 mol% or more and 40 mol% or less, 20 mol% or more 40 mol% Hereinafter, it may be prepared by reaction of a monomer compound for synthesizing a carbamic acid derivative polymer containing 30 mol% or more and 40 mol% or less or 35 mol% or more and 40 mol% or less, a chain extender, and a polycarbonate diol.

When the second repeating unit is contained in an amount of less than 50 mol% with respect to the total repeating units of the carbamic acid derivative polymer, the mechanical properties of the polymer film prepared from the carbamic acid derivative polymer may not be sufficiently implemented, and the carbamic acid derivative When the second repeating unit exceeds 85 mol% with respect to the total repeating unit of the polymer, the content of the hard segment of the carbamic acid derivative polymer is excessive, resulting in a technical problem of lowering the reliability of the polymer film produced therefrom. .

In addition, when the third repeating unit is contained in an amount of less than 10 mol% with respect to the total repeating units of the carbamic acid derivative polymer, the hard segment content of the carbamic acid derivative polymer may be excessive and the reliability of the polymer film produced therefrom may be reduced. And, when the third repeating unit exceeds 40 mol% with respect to the total repeating unit of the carbamic acid derivative polymer, the mechanical properties of the polymer film prepared from the carbamic acid derivative polymer may not be sufficiently implemented,

Therefore, by including the second repeating unit and the third repeating unit in the above-described range, the carbamic acid derivative polymer can implement excellent compression recovery performance.

Meanwhile, the carbamic acid derivative polymer according to an embodiment of the present invention contains 30 moles of a polyfunctional isocyanate compound based on the total number of moles of the monomer compound, chain extender, polycarbonate diol, and polyfunctional isocyanate compound for synthesizing the carbamic acid derivative polymer. % Or more and 70 mol% or less, 30 mol% or more and 65 mol% or less, 35 mol% or more and 65 mol% or less, 40 mol% or more and 50 mol% or less of the carbamic acid derivative polymer synthesis monomer compound, chain extender, poly It can be prepared by reaction of a carbonate diol and a polyfunctional isocyanate compound.

When the polyfunctional isocyanate-based compound is contained in an amount less than 30 mol% based on the total number of moles of the total reactants, the carbamic acid derivative polymer may not be sufficiently synthesized. The viscosity is too high, and the blendability with other compositions becomes significantly inferior, and thus, a technical problem in which gelation occurs may occur.

The method for preparing the carbamic acid derivative polymer of the embodiment is not limited. The synthesis reaction of the carbamic acid derivative polymer may be performed at a temperature of 40°C or more and 70°C or less. By controlling the reaction temperature within the above-described range, the carbamic acid derivative polymer can be stably polymerized, and the carbamic acid derivative polymer can be polymerized at a relatively low temperature, thereby reducing manufacturing cost and manufacturing time.

Ⅲ. Polymer resin composition

According to another embodiment of the present invention, a polymer resin composition including the carbamic acid derivative polymer is provided.

The polymer resin composition of the embodiment may include the carbamic acid derivative polymer; And an organic solvent.

The organic solvent is not very limited, but acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexane, toluene, xylene, ethylene glycol monomethyl ether (methyl cellosolve) and ethylene glycol monoethyl ether (ethyl cellosolve) It may include at least one of.

The polymer resin composition of the embodiment may have a solid content of 20% or more and 70% or less, 30% or more and 60% or less, 40% or more and 55% or less, or 40% or more and 41% or less. The solid content may mean a solute or solid material excluding a solvent in the entire solution, and specifically, the solid content of the polymer resin composition may refer to additives such as the carbamic acid derivative polymer and catalyst, excluding the organic solvent. When the solid content of the polymer resin composition is within the above-described range, the polymer resin composition may be thickly applied on a substrate, and the thickness of the polymer film may be easily adjusted through this.

In the polymer resin composition of the embodiment, the content of the organic solvent may be 30 parts by weight or more and 80 parts by weight or less based on 100 parts by weight of the carbamic acid derivative polymer. By adjusting the content of the organic solvent within the above-described range, the solid content of the polymer resin composition can be controlled and the coatability of the polymer resin composition can be improved.

The polymer resin composition of the above embodiment may further include additives such as a catalyst, a crosslinking agent, a UV absorber, and a filler.

Specifically, the catalyst may be an amine-based catalyst and/or a metal catalyst. Specifically, the amine-based catalyst may include at least one of a monoamine compound, a diamine compound, a triamine compound, a polyamine compound, a cyclic amine compound, an alcohol amine compound, and an ether amine compound. In addition, the metal catalyst may include at least one of a nickel-based compound, an organic tin compound, an organic bismuth compound, an organic lead compound, an organic nickel compound, and an organic zinc compound. More specifically, the catalyst may be dibutyltin dilaurate.

The polymer resin composition of the embodiment may include 0.001% by weight or more and 0.1% by weight or less, 0.001% by weight or more and 0.05% by weight or less, or 0.005% by weight or more and 0.02% by weight or less based on the total weight of the polymer resin composition. .

Meanwhile, the crosslinking agent may be a compound containing at least two or more functional groups capable of reacting with an isocyanate group. Specifically, the crosslinking agent is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, triethanolamine, and pentaerythritol It may include at least one of.

In addition, the polymer resin composition of the embodiment may further include a dye. The dye may express the color of the polymer film including the cured product of the polymer resin composition. As the dye, those used as dyes in the art may be used without limitation, and for example, carbon black may be used.

On the other hand, the polymer resin composition of the embodiment may further include a UV absorber. Specifically, the polymer resin composition may further include less than 0.001% by weight of a UV absorber based on the total weight of the polymer resin composition in addition to the carbamic acid derivative polymer. The term less than 0.001% by weight may mean that it does not include at all, or includes only a very small amount of 0.00001% by weight or more and less than 0.001% by weight.

When the polymer resin composition contains more than 0.001% by weight of the UV absorber, the compatibility between the UV absorber and the polymer resin is poor, so that not only agglomeration occurs in the composition, but also agglomeration occurs in the polymer film prepared therefrom. In addition, there may be a technical problem that not only decreases the UV blocking ability, but also results in poor durability of the product.

That is, in the polymer resin composition of the embodiment, the UV absorber is less than 0.001% by weight, and the UV absorber is not included or is contained in a very small amount even if it is included, thereby realizing excellent UV blocking ability and improving the durability of the product. Can be implemented.

IV. Polymer film

According to another embodiment of the present invention, a polymer film including a cured product of a polymer resin composition is provided.

The cured product means a material obtained through the curing process of the polymer resin composition of the embodiment.

As the polymer film includes the cured product of the polymer resin composition of the above-described embodiment, it may exhibit excellent reliability and UV-blocking ability, as well as excellent optical properties and durability.

Although the thickness of the polymer film is not largely limited, for example, it can be freely adjusted within the range of 0.001 µm to 100 µm. When the thickness of the polymer film increases or decreases by a specific value, physical properties measured in the polymer film may also change by a certain value.

Although the example of the method of manufacturing the polymer film is not largely limited, for example, applying the polymer resin composition of the other embodiment to a substrate to form a coating film (step 1); Drying the coating film (step 2); And hardening the dried coating film by heat treatment (step 3).

Step 1 is a step of forming a coating film by applying the above-described polymer resin composition to a substrate. The contents of the polymer resin composition include all the contents described above in the embodiment.

A method of applying the polymer resin composition to the substrate is not particularly limited, and for example, a method such as screen printing, offset printing, flexo printing, inkjet, etc. may be used.

Step 2 is a step of drying a coating film formed by applying the polymer resin composition to a substrate. The drying step of the coating film may be performed by a heating means such as a hot plate, a hot air circulation furnace, or an infrared furnace, and may be performed at a temperature of 50°C to 150°C, or 100°C to 150°C.

Step 3 is a step of curing the dried coating film by heat treatment. In this case, the heat treatment may be performed by a heating means such as a hot plate, a hot air circulation furnace, or an infrared furnace, and may be performed at a temperature of 180°C to 250°C, or 190°C to 220°C.

On the other hand, the polymer film of the embodiment has a transmittance of 15% or less, 0.01% or more, 13% or less, 0.70% or more, for ultraviolet rays having a wavelength of 410 nm measured using a UV-vis spectroscopy (Agillent, UV 8453) device. It may be 13% or less, 0.70% or more and 5% or less, or 0.70% or more and 1% or less.

In the case of a polymer film containing a UV blocker applied in the form of an additive in the related art, there was a problem in that the blocking ability was significantly deteriorated in the case of UV having a wavelength of 400 nm or more while blocking UV having a wavelength of 200 nm to 400 nm. As the polymer film of the embodiment includes the carbamic acid derivative polymer synthesized from the monomer compound for synthesizing the carbamic acid derivative polymer of the embodiment described above, it implements remarkably excellent UV blocking ability even for ultraviolet rays having a wavelength of 410 nm, which is a wavelength of 400 nm or more. Thus, it is possible to implement excellent UV blocking ability even in the ultraviolet region of a long wavelength.

Meanwhile, the polymer film of the embodiment has a value of b measured according to the measurement method of ASTM E313 using a Shimadzu UV-2600 UV-vis spectrometer of 9.0 or less, 8.0 or less, 4.0 or more and 8.0 or less, 4.26 or more and 7.29 or less, 4.26 or more It may be 6.0 or less or 4.26 or more and 5.00 or less.

Since the polymer film of one embodiment includes the carbamic acid derivative polymer synthesized from the monomer compound for synthesizing the carbamic acid derivative polymer of the above-described embodiment, the b value is 9.0 or less, thereby implementing excellent optical properties.

Ⅴ. Automotive parts

According to another embodiment of the present invention, a component for an automobile including the polymer film is provided.

The polymer film may be introduced into automobile parts or the like by a known method. The polymer film is prepared from the carbamic acid derivative polymer synthesized from the monomer compound for synthesizing the carbamic acid derivative polymer of the embodiment, and thus, excellent stability can be realized with excellent general properties. Accordingly, it is possible to provide automotive parts that can exhibit high reliability and durability.

The example of the automotive part is not limited, but may be introduced, for example, to a paint protection film (PPF) for an automobile.

According to the present invention, a monomer compound for synthesizing a carbamic acid derivative polymer capable of realizing excellent UV-blocking ability and optical properties, and achieving high reliability and durability, a carbamic acid derivative polymer, a polymer film containing the same, and a vehicle including the same Parts can be provided.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention. However, the following examples are provided for easier understanding of the present invention, and the content of the present invention is not limited thereby.

[Synthesis Example and Comparative Synthesis Example]

Synthesis Example: Preparation of Compound A

Compound a (30.00 g, 21.72 mmol) and potassium carbonate (65.9 g, 47.78 mmol) were dissolved in 150 ml of dimethylformamide, and then 6-chloro-1-hexanol (59.36 g, 45.61 mmol) was slowly added dropwise for 24 hours. It was stirred at 95 °C. After the reaction was terminated, the temperature was lowered to room temperature, recrystallized twice with water and DMF, and vacuum dried to prepare the compound A (61.54g, yield 83.72%).

Comparative Synthesis Example: Preparation of Compound E

Compound E (52.41g, yield 55.66%) was prepared in the same manner as in Synthesis Example, except that 2-chloroethanol was added instead of 6-chloro-1-hexanol.

* [Examples 1 to 2: Preparation of diol monomer]

Example 1: Preparation of Compound B

Compound A (15.00g, 4.43mmol) and ethyl cyanoacetate (5.51g, 4.87mmol) of the Synthesis Example were dissolved in 50 ml of ethanol, and then piperidine (0.38g, 0.44mmol) was slowly added dropwise to 50 for 8 hours. It was stirred at °C. After the reaction was terminated, the temperature was lowered to room temperature, recrystallized twice in water and ethanol, and dried under vacuum to prepare Compound B (16.47g, yield 85.71%).

Example 2: Preparation of Compound C

Compound A (37.26g, 11.00mmol) and malononitrile (8.00g, 12.11mmol) of the Synthesis Example were dissolved in 100ml of ethanol, and then piperidine (0.94g, 1.10mmol) was slowly added dropwise at 50° C. for 8 hours. Stirred at. After the reaction was terminated, the temperature was lowered to room temperature, recrystallized twice in water and ethanol, and vacuum dried to prepare the compound C (38.47g, yield 90.41%).

[Comparative Examples 1 to 2: Preparation of diol monomer]

Comparative Example 1: Preparation of Compound F

Compound F (12.24g, yield 86.17%) was prepared in the same manner as in Example 1, except that Compound E of Comparative Synthesis Example was added instead of Compound A of Synthesis Example.

Comparative Example 2: Preparation of Compound G

Compound G (10.98g, yield 90.56%) was prepared in the same manner as in Example 2, except that Compound E of Comparative Synthesis Example was added instead of Compound A of Synthesis Example.

[Examples 3 to 5: Preparation of polyurethane copolymer and polyurethane film]

Example 3

(1) Preparation of polyurethane copolymer

As a monomer, 1.2 mmol of the compound B of Example 1, 29.6.mmol of polycarbonatediol (PCDL) having a number average molecular weight of 1,000 g/mol from Asahi Kasei, 1,4-butanediol from BASF as a chain extender ( 1,4-butanediol; 1,4BD) 46.3 mmol, 74.1 mmol of Evonik's isophorone diisocyanate (IPDI) was used as an isocyanate-based hardener, and methyl ethyl ketone was used as an organic solvent. After dissolving a monomer, a chain extender, and an isocyanate-based curing agent in methyl ethyl ketone, it was charged into the reactor. After heating and maintaining the charged raw material to 52° C., 0.01 weight of dibutyl tin dilaurate (DBDTL) as a catalyst based on 100 parts by weight of a total of 100 parts by weight of the raw material of the monomer, chain extender, and isocyanate-based hardener Part was added to the organic solvent and reacted at 62° C. for 9 hours to prepare a polyurethane composition containing a polyurethane copolymer. After the reaction was completed, the temperature of the reactor was cooled to 40° C. and dilution was performed with toluene. The weight average molecular weight of the prepared polyurethane copolymer was 46,120 g/mol, and the solid content of the polyurethane composition was 40.54 wt%.

(2) Preparation of polyurethane film

The polyurethane composition was coated on a polyester film and then cured at a high temperature in the range of about 120° C. to 150° C. in a reaction curing machine to prepare a polyurethane film having a thickness of 1.0 mm.

Example 4

As shown in Table 1 below, a polyurethane copolymer and a polyurethane film were prepared in the same manner as in Example 4, except that 2.4 mmol of Compound B of Example 1 was used as a monomer. The weight average molecular weight of the prepared polyurethane copolymer was 39,600 g/mol, and the solid content of the polyurethane composition was 40.81 wt%.

Example 5

As shown in Table 1 below, a polyurethane copolymer and a polyurethane in the same manner as in Example 4, except that 1.2 mmol of compound C of Example 2 was used instead of 1.2 mmol of compound B of Example 1 as a monomer. The film was prepared. The weight average molecular weight of the prepared polyurethane copolymer was 45,657 g/mol, and the solid content of the polyurethane composition was 40.69 wt%.

[Comparative Examples 3 to 5: Preparation of polyurethane copolymer and polyurethane film]

Comparative Example 3

As shown in Table 1 below, a polyurethane copolymer and a polyurethane in the same manner as in Example 4, except that 1.2 mmol of the compound F of Comparative Example 1 was used instead of 1.2 mmol of the compound B of Example 1 as a monomer. The film was prepared. The weight average molecular weight of the prepared polyurethane copolymer was 41,7792 g/mol, and the solid content of the polyurethane composition was 40.25 wt%.

Comparative Example 4

As shown in Table 1 below, a polyurethane copolymer and a polyurethane in the same manner as in Example 4, except that 1.2 mmol of Compound G of Comparative Example 2 was used instead of 1.2 mmol of Compound B of Example 1 as a monomer. The film was prepared. The weight average molecular weight of the prepared polyurethane copolymer was 39,084 g/mol, and the solid content of the polyurethane composition was 39.93 wt%.

Comparative Example 5

(1) Preparation of polyurethane copolymer

As a monomer, 56.2 mmol of polycarbonatediol (PCDL) with a number average molecular weight of 1,000 g/mol from Asahi Kasei, 89.4 mmol of 1,4-butanediol (1,4BD) from BASF as a chain extender , As an isocyanate-based curing agent, 140.5 mmol of Evonik's diisocyanate diisocyanate (IPDI) was used, and methyl ethyl ketol was used as an organic solvent. After dissolving a monomer, a chain extender and an isocyanate-based curing agent in methyl ethyl ketone, it was charged into the reactor. After heating and maintaining the charged raw material to 52° C., 0.01 parts by weight of dibutyl tin dilaurate (DBDTL) as a catalyst based on 100 parts by weight of the total raw materials of the monomer, chain extender, and isocyanate-based curing agent. It was added to an organic solvent and reacted at 62° C. for 9 hours to prepare a polyurethane composition containing a polyurethane copolymer. After the reaction was completed, the temperature of the reactor was cooled to 40° C., and dilution was performed using toluene. The weight average molecular weight of the prepared polyurethane copolymer was 45,340 g/mol.

1.05 mmol of Compound A of Synthesis Example was added to the polyurethane composition afterwards, and mixed to prepare a polyurethane composition having a solid content of 40.59 wt%.

(2) Preparation of polyurethane film

The polyurethane composition was coated on a polyester film and then cured at a high temperature in the range of about 120° C. to 150° C. in a reaction curing machine to prepare a polyurethane film having a thickness of 1.0 mm.

Monomer
(mmol) Chain extender
(mmol) Hardener (mmol) catalyst UV absorber (mmol) Example 3 PCDL (29.6) + Compound B (1.2) 1,4BD
(46.3) IPDI
(74.1) DBTDL
(100ppm) - Example 4 PCDL (29.6) + Compound B (2.4) 1,4BD(46.3) IPDI
(74.1) DBTDL
(100ppm) - Example 5 PCDL (29.6) + compound C (1.2) 1,4BD(46.3) IPDI
(74.1) DBTDL
(100ppm) - Comparative Example 3 PCDL (29.6) + compound F (1.2) 1,4BD(46.3) IPDI
(74.1) DBTDL
(100ppm) - Comparative Example 4 PCDL (29.6) + compound G (1.2) 1,4BD(46.3) IPDI
(74.1) DBTDL
(100ppm) - Comparative Example 5 PCDL(29.6) 1,4BD(46.3) IPDI
(74.1) DBTDL
(100ppm) Compound A
(1.2)

<Experimental Example> 1. Solubility

With respect to the monomers of Examples 1 to 2 and Comparative Examples 1 to 2, a supersaturated solution was prepared by adding an excess to a 60°C solvent (ethyl acetate), and maintained at 25°C for 1 hour in a constant temperature water bath to prepare a saturated solution. After removing the solvent by taking 5 g of a saturated solution, the weight of the residual UV monomer was measured. The solubility of the monomer was calculated through Equation 1 below.

[Equation 1]

Solubility = Weight of residual UV monomer (g) / Weight of saturated solution (g) × 100.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Solubility 25.64 27.11 3.71 0.29

2. Transmittance The films prepared in Examples 3 to 5 and Comparative Examples 3 to 5 were 380 nm, 390 nm, 400 nm, 410 nm, 420 nm, 430 nm using a UV-vis spectroscopy (Agillent, UV 8453) device. And transmittance for 440 nm was measured.

3. Color difference

The films prepared in Examples 3 to 5 and Comparative Examples 3 to 5 were prepared with a sample size of 5 cm * 5 cm, and the brightness index (L), color coordinates (a, b), and yellow index (YI) were calculated for the sample. It was measured using a Shimadzu UV-2600 UV-vis spectrometer.

Specifically, the brightness index (L) and the color coordinates (a, b) denote values of the coordinate axis representing a unique color, respectively. L has a value of 0 to 100, and the closer to 0 is, the more black it is, and the closer to 100, the more white is. A has positive (+) and negative (-) values based on 0, positive (+) means red, and negative (-) means green. b has positive (+) and negative (-) values based on 0, and positive (+) means yellow, and negative (-) means blue.

The brightness index (L) and color coordinates (a, b) were measured according to the measurement method of ASTM E313 using a Shimadzu UV-2600 UV-vis spectrometer.

Transmittance(%) brightness
Index (L) Color coordinate (a) Color coordinate (b) 380 390 400 410 420 430 440 Example 3 0.01 0.19 0.07 12.78 69.69 93.02 97.06 93.18 -2.12 4.26 Example 4 0.01 0.18 0.16 4.76 58.18 88.55 93.84 95.93 -2.82 5.73 Example 5 0.01 0.19 0.18 0.78 34.08 84.01 95.81 95.23 -3.48 7.29 Comparative Example 3 0.01 0.14 2.57 42.24 88.01 98.84 99.80 95.78 -1.51 2.85 Comparative Example 4 0.01 0.18 0.17 8.60 40.76 64.71 76.68 93.62 -3.18 9.58 Comparative Example 5 0.01 0.16 0.03 16.77 72.51 92.68 95.82 94.54 -1.63 3.36

As shown in Table 2, the monomer compounds of Examples 1 to 2 of the present invention have a solubility in ethyl acetate of 16.07 or higher, and the solubility in an organic solvent is remarkably compared to the comparative example in which the solubility is measured to be 10 or less. In addition, in the case of Compound G used in Comparative Example 2, not only the polymer resin was cloudy due to its low solubility, but also showed a result that the overall transmittance was low even when prepared in a film form.

In addition, as shown in Table 3, it was confirmed that the polymer films of Examples 3 to 5 of the present invention exhibited excellent UV blocking ability and excellent optical properties as compared to the polymer films of Comparative Examples.

Specifically, the polymer films of Examples 3 to 5 of the present invention have excellent transmittances of 0.18% or less for ultraviolet rays at a wavelength of 400 nm, 12.78% or less for ultraviolet rays at 410 nm, and 69.69% or less for ultraviolet rays at 420 nm. It showed an ultraviolet blocking ability, and the b value was measured to be 7.29 or less, and showed excellent optical properties.

On the other hand, it was confirmed that the polymer films of Comparative Examples 3 to 5 had transmittances of 16.77% or more for ultraviolet rays of 410 nm and 72.51% or more for ultraviolet rays of 420 nm, indicating inferior ultraviolet blocking ability.

In addition, in the case of the polymer film of Comparative Example 4 using the diol monomer of Comparative Example 2, the yellowness was measured to be 9.58, it was confirmed that it exhibited inferior optical properties compared to the present Example.

Claims (17)

A monomer compound for synthesizing a carbamic acid derivative polymer represented by the following Formula 1:
[Formula 1]

In Formula 1,
D ₁ is -OH or -NH ₂ ,
T ₁ is a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO ₂ -, -CONH-, -N(R ₁ )-, -P(R ₂ )- Is any one of,
R ₁ and R ₂ is each independently one of hydrogen or a hydrocarbon-based monovalent functional group having 1 to 10 carbon atoms,
L ₁ is a hydrocarbon-based divalent functional group having 3 or more and 10 or less carbon atoms,
Y is a monovalent functional group containing a conjugate structure,
n is an integer of 2 to 5.
The method of claim 1,
In Y of Formula 1, a monovalent functional group containing a conjugate structure is represented by the following Formula 2, a monomer compound for synthesizing a carbamic acid derivative polymer:
[Formula 2]

In Chemical Formula 2,
A ₁ is _one of hydrogen or a hydrocarbon-based monovalent functional group,
A ₂ and A ₃ is each independently a cyano group, -(C=O)-NR ₄ R ₅ or -(C=O)-OR ₆ ,
R _4, R ₅ and Each of R ₆ is independently one of an alkyl group having 1 or more and 10 or less carbon atoms, an alkenyl group having 2 or more and 10 or less carbon atoms, or an alkynyl group having 2 or more and 10 or less carbon atoms.
The method of claim 2,
Wherein A ₂ and of formula (II) At least one or more of A ₃ is a cyano group, and the others are -(C=O)-OR ₆ ,
R ₆ is one of an alkyl group having 1 or more and 10 or less carbon atoms, an alkenyl group having 2 or more and 10 or less carbon atoms, or an alkynyl group having 2 or more and 10 or less carbon atoms,
A monomer compound for synthesizing a carbamic acid derivative polymer.
The method of claim 1,
L ₁ in Formula 1 is a linear or branched alkylene group having 3 to 10 carbon atoms, a monomer compound for synthesizing a carbamic acid derivative polymer.
The method of claim 1,
The monomer compound for synthesizing the carbamic acid derivative polymer is represented by the following Formula 1-1, a monomer compound for synthesizing the carbamic acid derivative polymer:
[Formula 1-1]

In Formula 1-1,
D ₂ and D ₃ are each independently -OH or -NH ₂ ,
T ₂ and T ₃ are each independently a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO ₂ -, -CONH-, -N(R ₁ )-,- Is any one of P(R ₂ )-,
R ₁ and R ₂ is each independently one of hydrogen or a hydrocarbon-based monovalent functional group having 1 to 10 carbon atoms,
L ₂ and L ₃ are each independently a hydrocarbon-based divalent functional group having 3 or more and 10 or less carbon atoms,
Y is a monovalent functional group containing a conjugate structure.
The method of claim 1,
The monomer compound for synthesizing the carbamic acid derivative polymer is one of the compounds represented by the following Formulas 1-2 to 1-3, the monomer compound for synthesizing the carbamic acid derivative polymer:
[Formula 1-2]

[Formula 1-3]

.
Carbamic acid derivative polymer comprising a first repeating unit represented by the following formula (3):
[Chemical Formula 3]

In Chemical Formula 3,
X ₁ and X ₂ are each independently -O- or -NH-,
L _4, L _5, L ₆ and L'are each independently a hydrocarbon-based divalent functional group having 3 or more and 10 or less carbon atoms,
T ₄ , T ₅ and T'is each independently a single bond, -O-, -CO-, -COO-, -S-, -SO-, -SO ₂ -, -CONH-, -N(R ₉ )-, -P(R ₁₀ )- is any one of,
R ₉ and R ₁₀ is each independently hydrogen or any one of a hydrocarbon-based monovalent functional group having 1 to 10 carbon atoms,
D'is -OH or -NH ₂ ,
Y ₁ is a monovalent functional group containing a conjugate structure,
n'is an integer of 0 to 3.
The method of claim 7,
The monovalent functional group containing the conjugate structure is represented by the following formula (2), a carbamic acid derivative polymer:
[Formula 2]

In Chemical Formula 2,
A ₁ is _one of hydrogen or a hydrocarbon-based monovalent functional group,
A ₂ and A ₃ is each independently a cyano group, -(C=O)-NR ₄ R ₅ or -(C=O)-OR ₆ ,
R _4, R ₅ and Each of R ₆ is independently one of an alkyl group having 1 or more and 10 or less carbon atoms, an alkenyl group having 2 or more and 10 or less carbon atoms, or an alkynyl group having 2 or more and 10 or less carbon atoms.
The method of claim 7,
A carbamic acid derivative polymer containing 0.1 mol% or more and 10 mol% or less of the first repeating unit with respect to all repeating units of the carbamic acid derivative polymer.
The method of claim 7,
A second repeating unit represented by the following formula (4); Or a carbamic acid derivative polymer further comprising a third repeating unit represented by the following formula (5):
[Formula 4]

[Formula 5]

In Chemical Formula 4 and Chemical Formula 5,
X ₃ to X ₆ are each independently -O- or -NH-,
L ₇ to L ₁₁ are each independently a hydrocarbon-based divalent functional group having 1 to 20 carbon atoms,
m is an integer of 1 or more.
The method of claim 10,
For all repeating units of the carbamic acid derivative polymer
The second repeating unit is included in an amount of 50 mol% or more and 85 mol% or less,
The third repeating unit is contained in an amount of 10 mol% or more and 40 mol% or less.
A polymer resin composition comprising the carbamic acid derivative polymer of claim 7.
The method of claim 12,
The polymer resin composition further comprises less than 0.001% by weight of a UV absorber based on the total weight of the polymer resin composition in addition to the carbamic acid derivative polymer.
A polymer film comprising a cured product of the polymer resin composition of claim 12.
The method of claim 14,
The polymer film has a transmittance of 15% or less for ultraviolet rays having a wavelength of 410 nm, a polymer film.
The method of claim 14,
The polymer film has a b value of 9.0 or less measured by a color difference meter.
A component for an automobile comprising the polymer film of claim 14.