KR102320096B1 - Alkylether-based urethane acrylate copolymer for 3d printing and method of preparing same - Google Patents

Abstract

Disclosed are an alkylether-based urethane acrylate copolymer for use in 3D printing and a method for manufacturing the same. The urethane acrylate copolymer is represented by structural formula 1, and by including PDMS, has excellent elasticity and stretchability, and also has excellent light transmittance and curing speed.

Description

Alkylether-based urethane acrylate copolymer for use in 3D printing and method for preparing the same

The present invention relates to an alkyl ether-based urethane acrylate copolymer for use in 3D printing and a method for preparing the same, and the urethane acrylate copolymer of the present invention includes poly(dimethylsiloxane) (PDMS), which has high transparency and a curing rate. is excellent

The current 3D printer market has a large market size in the consumer/home appliance field, the medical field, and the automobile field, and it is expected that the market ratio of the automobile field and the aviation field will increase significantly in the future. As interest and demand for 3D printing are growing in various fields such as medical and art as well as industrial fields such as automobiles and aviation, the supply of domestic 3D printers and materials is required.

If 3D printing technology is used for the rear combination lamp among auto parts, it is expected that it will be possible to enter the market by making precise production in a shorter time than other manufacturing technologies.

Conventional urethane acrylate for 3D printing and a composition thereof have a problem in that transparency and hardness are weak, and research on urethane acrylate for 3D printing and a composition thereof having excellent transparency and hardness is required.

An object of the present invention is to solve the above problems, to provide a urethane acrylate copolymer for 3D printing excellent in transparency and hardness, a method for producing the same, and a film composition comprising the same.

According to one aspect of the present invention, a urethane acrylate copolymer represented by Structural Formula 1 is provided.

[Structural Formula 1]

In Structural Formula 1,

또는

이고,R ¹ is

or

ego,

R ⁴ and R ⁵ are each independently a hydrogen atom or a C1 to C5 alkyl group,

p is any one of integers from 1 to 3,

R ⁶ to R ⁸ are each independently a hydrogen atom or a C1 to C5 alkyl group,

R ² are each independently a C1 to C5 alkylene group,

R ³ is each independently a hydrogen atom or a C1 to C5 alkyl group,

n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,

n ₂ is any one of an integer from 1 to 1,000,

이고,A is

ego,

R ⁹ is a C1 to C6 alkylene group,

q is any one of an integer from 1 to 100,

이고,B is

ego,

R ¹⁰ is each independently a C1 to C5 alkylene group,

R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a C1 to C5 alkyl group,

r is an integer from 1 to 100.

또는

이고,In addition, R ¹ is

or

ego,

R ⁴ and R ⁵ are each independently a hydrogen atom or a C1 to C3 alkyl group,

p is any one of integers from 1 to 3,

R ⁶ to R ⁸ are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ² are each independently a C1 to C3 alkylene group,

R ³ is each independently a hydrogen atom or a C1 to C3 alkyl group,

n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,

n ₂ is any one of an integer from 1 to 1,000,

이고,A is

ego,

R ⁹ is a C3 to C5 alkylene group,

q is any one of an integer from 1 to 100,

이고,B is

ego,

R ¹⁰ is each independently a C2 to C4 alkylene group,

R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a C1 to C3 alkyl group,

r may be an integer from 1 to 100.

또는

이고,In addition, R ¹ is

or

ego,

R ⁴ and R ⁵ are each independently a hydrogen atom or a C1 to C2 alkyl group,

p is 1 or 2,

R ⁶ to R ⁸ are each independently a hydrogen atom or a C1 to C2 alkyl group,

R ² are each independently a C1 to C2 alkylene group,

R ³ is each independently a hydrogen atom or a C1 to C2 alkyl group,

n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,

n ₂ is any one of an integer from 1 to 1,000,

이고,A is

ego,

R ⁹ is a C4 alkylene group,

q is any one of an integer from 1 to 100,

이고,B is

ego,

R ¹⁰ is a C3 alkylene group,

R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a C1 to C2 alkyl group,

r may be an integer from 1 to 100.

또는

이고,In addition, R ¹ is

or

ego,

R ⁴ and R ⁵ are hydrogen atoms,

p is 1,

R ⁶ to R ⁸ are C1 alkyl groups,

R ² is a C2 alkylene group,

R ³ is a C1 alkyl group,

n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,

n ₂ is any one of an integer from 1 to 1,000,

이고,A is

ego,

R ⁹ is a C4 alkylene group,

q is any one of an integer from 1 to 100,

이고,B is

ego,

R ¹⁰ is a C3 alkylene group,

R ¹¹ to R ¹⁴ are C1 alkyl groups,

r may be an integer from 1 to 100.

In addition, the compound represented by Structural Formula 1 may be a compound represented by Structural Formula 2 below.

[Structural Formula 2]

In Structural Formula 2,

이고,A is

ego,

q is any one of an integer from 1 to 100,

이고,B is

ego,

r is any one of an integer from 1 to 100,

n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,

n ₂ is any one of an integer from 1 to 1,000.

In addition, the urethane acrylate copolymer may be used for 3D printing.

According to another aspect of the present invention, the urethane acrylate copolymer; And radical initiator; is provided a urethane acrylate copolymer composition comprising.

In addition, the urethane acrylate copolymer composition may include 0.1 to 10 parts by weight of the radical initiator based on 100 parts by weight of the urethane acrylate copolymer.

In addition, the radical initiator is 1-hydroxy-cyclohexyl-phenyl-ketone (1-Hydroxycyclohexyl-phenyl-ketone, IRGACURE 184), camphoquinone (camphoquinone), ethyl-4-dimethylaminobenzoate (ethyl-4-dimethylamino) benzoate), tertiary amine initiator, diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, tolylcumyliodoniumtetrakis(pentafluorophenyl)borate, acyl, bisacyl phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide, Bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one, bis(2,4,6-trimethyl benzoyl) phenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one and ethyl 2,4,6-trimethylbenzylphenyl phosphinate can

In addition, the urethane acrylate copolymer composition may be for use in 3D printing.

According to another aspect of the present invention, there is provided a molded article prepared by 3D printing and crosslinking the urethane acrylate copolymer composition.

According to another aspect of the present invention, (a) compound 11 represented by Structural Formula 11 and compound 12 represented by Structural Formula 12 of an excess isocyanate group equivalent based on the hydroxyl group equivalent of Compound 11 are urethane-reacted to obtain Structural Formula 13 preparing a mixture 1 including the represented compound 13 and unreacted compound 12; (b) urethane reaction of Compound 14 represented by Structural Formula 14 with an excess hydroxy group equivalent based on the isocyanate group equivalent of Compound 13 with Mixture 1 to obtain a mixture 2 comprising compound 15 and unreacted compound 14 represented by Structural Formula 15 manufacturing; (c) urethane reaction of Compound 12 represented by Structural Formula 12 with an excess isocyanate group equivalent based on the hydroxyl group equivalent of Compound 15 with the above mixture 2 to obtain a mixture 3 comprising compound 16 and unreacted compound 12 represented by Structural Formula 16 manufacturing; and (d) preparing a compound represented by Structural Formula 1 by urethane-reacting Compound 17 represented by Structural Formula 17 with an excess hydroxyl group equivalent based on the isocyanate group equivalent of Compound 16 with the mixture 3 to prepare a compound represented by Structural Formula 1; Urethane acrylate containing A method for preparing the copolymer is now provided.

[Scheme 1]

In Scheme 1,

또는

이고,R ¹ is

or

ego,

R ⁴ and R ⁵ are each independently a hydrogen atom or a C1 to C5 alkyl group,

p is any one of integers from 1 to 3,

R ⁶ to R ⁸ are each independently a hydrogen atom or a C1 to C5 alkyl group,

R ² are each independently a C1 to C5 alkylene group,

R ³ is each independently a hydrogen atom or a C1 to C5 alkyl group,

n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,

n ₂ is any one of an integer from 1 to 1,000,

이고,A is

ego,

R ⁹ is a C1 to C6 alkylene group,

q is any one of an integer from 1 to 100,

이고,B is

ego,

R ¹⁰ is each independently a C1 to C5 alkylene group,

R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a C1 to C5 alkyl group,

r is an integer from 1 to 100.

In addition, the step (a) may include 101 to 300 equivalents of the isocyanate group of the compound 12 represented by the structural formula 12 based on 100 equivalents of the hydroxyl group of the compound 11 represented by the structural formula 11.

In addition, the step (b) may include 101 to 300 equivalents of the hydroxyl group of the compound 14 represented by the Structural Formula 14 based on 100 equivalents of the isocyanate group of the compound 13 represented by the Structural Formula 13.

In addition, the step (c) may include 101 to 300 equivalents of the isocyanate group of the compound 12 represented by the structural formula 12 based on 100 equivalents of the hydroxyl group of the compound 15 represented by the structural formula 15.

In addition, the step (d) may include 101 to 300 equivalents of the hydroxyl group of the compound 17 represented by the structural formula 17 based on 100 equivalents of the isocyanate group of the compound 16 represented by the structural formula 16.

In addition, the reaction of steps (a) to (d) may use dibutyltin dilaurate (DBTDL) as a catalyst.

In addition, the reaction of steps (a) to (c) may be each independently performed at a temperature of 30 to 100 °C, and the reaction of step (d) may be performed at a temperature of 30 to 45 °C.

In addition, the reaction of steps (a) to (d) may be performed by solution polymerization using a solvent.

In addition, the solvent may include at least one selected from the group consisting of tetrahydrofuran (THF), toluene, dimethylformamide (DMF), and acetone.

The urethane acrylate copolymer and the urethane acrylate copolymer film including the urethane acrylate copolymer of the present invention include poly(dimethylsiloxane) (PDMS) modified inside the urethane acrylate copolymer, so that transparency and hardness are excellent.

These drawings are for reference in describing an exemplary embodiment of the present invention, and the technical spirit of the present invention should not be construed as being limited to the accompanying drawings.
1 shows the FT-IR results measured when preparing a hydroxyl-terminated PDMS according to Preparation Example 1.
2 shows the results of H-NMR analysis of the material prepared according to Preparation Example 1.
FIG. 3a shows FT-IR results when IPID was first added dropwise to hydroxyl-terminated PDMS when preparing a urethane acrylate copolymer according to Example 1. FIG.
FIG. 3b shows FT-IR results when PTMG is added dropwise to a compound having an IPID as a terminal when preparing a urethane acrylate copolymer according to Example 1. FIG.
FIG. 3c shows FT-IR results when IPID is added dropwise to a compound having PTMG as a terminal when preparing a urethane acrylate copolymer according to Example 1. FIG.
FIG. 3d shows FT-IR results when HEMA is added dropwise to a compound having an IPID as a terminal when preparing a urethane acrylate copolymer according to Example 1. FIG.
FIG. 4a shows FT-IR results when IPID was first added dropwise to PTMG when preparing a urethane acrylate copolymer according to Comparative Example 1. FIG.
FIG. 4b shows FT-IR results when IPID is added dropwise to a compound having PTMG as a terminal in the preparation of a urethane acrylate copolymer according to Comparative Example 1. FIG.
FIG. 4c shows FT-IR results when HEMA is added dropwise to a compound having an IPID as a terminal when preparing a urethane acrylate copolymer according to Comparative Example 1. FIG.
5 shows the results of GPC analysis of Example 1 and Comparative Example 1 using m-Cresol as a solvent.
6 is a schematic view showing a method for manufacturing a urethane acrylate copolymer film according to an embodiment of the present invention.
7 shows transmittance when the thickness of the films prepared according to Examples 2 to 4 and Comparative Examples 2 to 4 was 500 μm.
FIG. 8 is the same graph as that of FIG. 7, and for comparison of transmittance differences, each result value is displayed every 30 nm based on a wavelength.
9 shows the photo DSC analysis results of Examples 2 to 4 and Comparative Examples 2 to 4;
10a shows the photo DSC analysis results of Comparative Examples 2 to 4;
Figure 10b shows the photo DSC analysis results of Examples 2 to 4.
Figure 11a shows the photo DSC analysis results of Example 2 and Comparative Example 2.
Figure 11b shows the photo DSC analysis results of Example 3 and Comparative Example 3.
11c shows the photo DSC analysis results of Example 4 and Comparative Example 4.
12 is a graph showing the comparison of the pencil hardness values of Example 3 and Comparative Example 3.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art to which the present invention pertains can easily carry out the present invention.

However, the following description is not intended to limit the present invention to specific embodiments, and when it is determined that a detailed description of a related known technology may obscure the gist of the present invention in describing the present invention, the detailed description thereof will be omitted. .

The terminology used herein is only used to describe specific embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, element, or combination thereof described in the specification exists, but is one or more other features or It should be understood that the existence or addition of numbers, steps, acts, elements, or combinations thereof, is not precluded in advance.

In addition, terms including an ordinal number such as first, second, etc. to be used below may be used to describe various elements, but the elements are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

In addition, when it is said that a component is "formed" or "stacked" on another component, it may be formed or laminated directly attached to the front surface or one surface on the surface of the other component. It should be understood that other components may be present in the .

Hereinafter, an alkyl ether-based urethane acrylate copolymer for use in 3D printing of the present invention and a manufacturing method thereof will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

The present invention provides a urethane acrylate copolymer represented by Structural Formula 1.

[Structural Formula 1]

In Structural Formula 1,

또는

이고,R ¹ is

or

ego,

R ⁴ and R ⁵ are each independently a hydrogen atom or a C1 to C5 alkyl group,

p is any one of integers from 1 to 3,

R ⁶ to R ⁸ are each independently a hydrogen atom or a C1 to C5 alkyl group,

R ² are each independently a C1 to C5 alkylene group,

R ³ is each independently a hydrogen atom or a C1 to C5 alkyl group,

n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,

n ₂ is any one of an integer from 1 to 1,000,

이고,A is

ego,

R ⁹ is a C1 to C6 alkylene group,

q is any one of an integer from 1 to 100,

이고,B is

ego,

R ¹⁰ is each independently a C1 to C5 alkylene group,

R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a C1 to C5 alkyl group,

r is an integer from 1 to 100.

또는

이고,In addition, R ¹ is

or

ego,

R ⁴ and R ⁵ are each independently a hydrogen atom or a C1 to C3 alkyl group,

p is any one of integers from 1 to 3,

R ⁶ to R ⁸ are each independently a hydrogen atom or a C1 to C3 alkyl group,

R ² are each independently a C1 to C3 alkylene group,

R ³ is each independently a hydrogen atom or a C1 to C3 alkyl group,

n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,

n ₂ is any one of an integer from 1 to 1,000,

이고,A is

ego,

R ⁹ is a C3 to C5 alkylene group,

q is any one of an integer from 1 to 100,

이고,B is

ego,

R ¹⁰ is each independently a C2 to C4 alkylene group,

R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a C1 to C3 alkyl group,

r may be an integer from 1 to 100.

또는

이고,In addition, R ¹ is

or

ego,

R ⁴ and R ⁵ are each independently a hydrogen atom or a C1 to C2 alkyl group,

p is 1 or 2,

R ⁶ to R ⁸ are each independently a hydrogen atom or a C1 to C2 alkyl group,

R ² are each independently a C1 to C2 alkylene group,

R ³ is each independently a hydrogen atom or a C1 to C2 alkyl group,

n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,

n ₂ is any one of an integer from 1 to 1,000,

이고,A is

ego,

R ⁹ is a C4 alkylene group,

q is any one of an integer from 1 to 100,

이고,B is

ego,

R ¹⁰ is a C3 alkylene group,

R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a C1 to C2 alkyl group,

r may be an integer from 1 to 100.

또는

이고,In addition, R ¹ is

or

ego,

R ⁴ and R ⁵ are hydrogen atoms,

p is 1,

R ⁶ to R ⁸ are C1 alkyl groups,

R ² is a C2 alkylene group,

R ³ is a C1 alkyl group,

n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,

n ₂ is any one of an integer from 1 to 1,000,

이고,A is

ego,

R ⁹ is a C4 alkylene group,

q is any one of an integer from 1 to 100,

이고,B is

ego,

R ¹⁰ is a C3 alkylene group,

R ¹¹ to R ¹⁴ are C1 alkyl groups,

r may be an integer from 1 to 100.

In addition, the compound represented by Structural Formula 1 may be a compound represented by Structural Formula 2 below.

[Structural Formula 2]

In Structural Formula 2,

이고,A is

ego,

q is any one of an integer from 1 to 100,

이고,B is

ego,

r is any one of an integer from 1 to 100,

n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,

n ₂ is any one of an integer from 1 to 1,000.

In addition, the urethane acrylate copolymer may be used for 3D printing.

The present invention is the urethane acrylate copolymer; and a radical initiator; may provide a urethane acrylate copolymer composition comprising.

In addition, the urethane acrylate copolymer composition may include 0.1 to 10 parts by weight of the radical initiator based on 100 parts by weight of the urethane acrylate copolymer, preferably 0.5 to 8 parts by weight, more preferably 1 to 5 parts by weight It may contain parts by weight. When the radical initiator is less than 0.1 parts by weight, it is not preferable because there is difficulty in curing, and when it exceeds 10 parts by weight, there is no change in the curing rate and economic efficiency is lowered by using an unnecessarily large amount, which is not preferable.

In addition, the radical initiator is 1-hydroxy-cyclohexyl-phenyl-ketone (1-Hydroxycyclohexyl-phenyl-ketone, IRGACURE 184), camphoquinone (camphoquinone), ethyl-4-dimethylaminobenzoate (ethyl-4-dimethylamino) benzoate), tertiary amine initiator, diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, tolylcumyliodoniumtetrakis(pentafluorophenyl)borate, acyl, bisacyl phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide, Bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one, bis(2,4,6-trimethyl benzoyl) phenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one and ethyl 2,4,6-trimethylbenzylphenyl phosphinate and preferably 1-hydroxy-cyclohexyl-phenyl-ketone.

In addition, the urethane acrylate copolymer composition may be for use in 3D printing.

The present invention provides a molded article prepared by 3D printing and crosslinking the urethane acrylate copolymer composition.

The present invention relates to (a) compound 11 represented by Structural Formula 11 and compound 12 represented by Structural Formula 12 with an excess isocyanate group equivalent based on the hydroxyl group equivalent of Compound 11 by urethane reaction of Compound 13 represented by Structural Formula 13 and unreacted compound preparing a mixture 1 comprising 12; (b) urethane reaction of Compound 14 represented by Structural Formula 14 with an excess hydroxy group equivalent based on the isocyanate group equivalent of Compound 13 with Mixture 1 to obtain a mixture 2 comprising compound 15 and unreacted compound 14 represented by Structural Formula 15 manufacturing; (c) urethane reaction of Compound 12 represented by Structural Formula 12 with an excess isocyanate group equivalent based on the hydroxyl group equivalent of Compound 15 with the above mixture 2 to obtain a mixture 3 comprising compound 16 and unreacted compound 12 represented by Structural Formula 16 manufacturing; and (d) preparing a compound represented by Structural Formula 1 by urethane-reacting Compound 17 represented by Structural Formula 17 with an excess hydroxyl group equivalent based on the isocyanate group equivalent of Compound 16 with the mixture 3 to prepare a compound represented by Structural Formula 1; Urethane acrylate containing A method for preparing a copolymer is provided.

[Scheme 1]

In Scheme 1,

또는

이고,R ¹ is

or

ego,

R ⁴ and R ⁵ are each independently a hydrogen atom or a C1 to C5 alkyl group,

p is any one of integers from 1 to 3,

R ⁶ to R ⁸ are each independently a hydrogen atom or a C1 to C5 alkyl group,

R ² are each independently a C1 to C5 alkylene group,

R ³ is each independently a hydrogen atom or a C1 to C5 alkyl group,

n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,

n ₂ is any one of an integer from 1 to 1,000,

이고,A is

ego,

R ⁹ is a C1 to C6 alkylene group,

q is any one of an integer from 1 to 100,

이고,B is

ego,

R ¹⁰ is each independently a C1 to C5 alkylene group,

R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a C1 to C5 alkyl group,

r is an integer from 1 to 100.

In addition, the step (a) may include 101 to 300 equivalents of the isocyanate group of the compound 12 represented by the structural formula 12 based on 100 equivalents of the hydroxyl group of the compound 11 represented by the structural formula 11, preferably 150 to 250 equivalent, more preferably 180 to 230 equivalents. When the isocyanate group of the compound 12 is less than 101 equivalents, it is difficult to successfully form the compound 13 prepared according to step (a), so it is not preferable because it is difficult to prepare the urethane acrylate copolymer of the present invention, and it is not preferable to exceed 300 equivalents. In this case, the efficiency is reduced economically by using an unnecessarily large amount, and the excess unreacted compound 12 contained in the mixture 1 binds to the hydroxyl group of the compound 14 represented by the structural formula 14 in the following reaction (step b) to form a short chain As the oligomeric compound of

In addition, the step (b) may include 101 to 300 equivalents of the hydroxyl group of the compound 14 represented by the structural formula 14 based on 100 equivalents of the isocyanate group of the compound 13 represented by the structural formula 13, preferably 150 to 250 equivalent, more preferably 180 to 230 equivalents. When the hydroxyl group of the compound 14 is less than 101 equivalents, it is difficult to successfully form the compound 15 prepared according to step (b). In this case, the efficiency is reduced economically by using an unnecessarily large amount, and the excess unreacted compound 14 contained in the mixture 2 is combined with the isocyanate group of the compound 12 represented by the structural formula 12 in the following reaction (step c) to form a short chain As the oligomeric compound of

In addition, the step (c) may include 101 to 300 equivalents of the isocyanate group of the compound 12 represented by the structural formula 12 based on 100 equivalents of the hydroxyl group of the compound 15 represented by the structural formula 15, preferably 150 to 250 equivalent, more preferably 180 to 230 equivalents. When the isocyanate group of the compound 12 is less than 101 equivalents, it is difficult to successfully form the compound 16 prepared according to step (c), so it is not preferable because it is difficult to prepare the urethane acrylate copolymer of the present invention thereafter, and it is not preferable to exceed 300 equivalents. In this case, the efficiency is reduced economically by using an unnecessarily large amount, and the excess unreacted compound 12 contained in the mixture 3 binds to the hydroxyl group of the compound 17 represented by the structural formula 17 in the following reaction (step d) to form a short chain As the oligomeric compound of

In addition, the step (d) may include 101 to 300 equivalents of the hydroxyl group of the compound 17 represented by the structural formula 17 based on 100 equivalents of the isocyanate group of the compound 16 represented by the structural formula 16, preferably 150 to 250 equivalent, more preferably 180 to 230 equivalents. When the hydroxyl group of the compound 17 is less than 101 equivalents, it is undesirable because it is difficult to successfully form the compound represented by Structural Formula 1 prepared according to step (d), and when it exceeds 300 equivalents, by using an unnecessarily large amount It is undesirable because it is economically low in efficiency and acts as a factor impairing the physical properties of the target polymer by affecting the reduction in the degree of crosslinking in the photocuring reaction.

In addition, the reaction of steps (a) to (d) may use dibutyltin dilaurate (DBTDL) as a catalyst.

In addition, the reaction of steps (a) to (c) may be each independently performed at a temperature of 30 to 100 °C, preferably at a temperature of 40 to 60 °C. When the reactions of steps (a) to (c) are respectively carried out at less than 30 ° C, the reaction rate is remarkably low, which is undesirable. It is undesirable because it affects as an obstacle in synthesizing the target polymer.

In addition, the reaction of step (d) may be carried out at a temperature of 30 to 45 °C, preferably 35 to 42 °C, more preferably at a temperature of 40 °C. When the reaction of step (d) is carried out at less than 30° C., the reaction rate is undesirably low, and when it exceeds 45° C., it is not preferable because gelation proceeds.

In addition, the reaction of steps (a) to (d) may be performed by solution polymerization using a solvent.

In addition, the solvent may include at least one selected from the group consisting of tetrahydrofuran (THF), toluene, dimethylformamide (DMF) and acetone, preferably tetrahydrofuran. (THF).

[Example]

Hereinafter, a preferred embodiment of the present invention will be described. However, this is for illustrative purposes only, and the scope of the present invention is not limited thereto.

manufacturing example 1: hydroxyl group end PDMS ( PDMS - DPA ) Produce

A magnetic bar, 100 mL of toluene (Toluene, Sigma-Aldrich) was placed in a two-necked round flask, and N _{2 was} purged. A Reflux tube was installed in the round flask, 20.03 g of allyl alcohol (Dae Jung) was added, and the mixture was stirred for 5 minutes. Then, 20 μL of Platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisoloxane complex solution (Sigma-Aldrich) was diluted in 2 mL of toluene and added dropwise. After stirring for 5 minutes, 50 g of Hydride terminated PDMS (Sigma-Aldrich, Mn-580, PDMS-H) was added dropwise, and then the temperature was raised to 100° C. and FT-IR was measured. is shown.

Referring to Figure 1, Hydride terminated PDMS (PDMS- H) with allyl alcohol the reaction Si-H peak, ^as-is (2160 cm ¹⁾ peak disappears -OH ^- can be confirmed that the generation (3360 cm ^1). The reaction was carried out until the Si-H peak disappeared, and when the Si-H peak disappeared, it was cooled to room temperature, and then filtered using alumina and toulene to remove the Pt catalyst. Thereafter, the reaction was evaporated at a temperature of 70°C to remove ally alcohol and toluene remaining after the reaction to prepare hydroxyl-terminated PDMS (PDMS-DPA).

2 shows the results of H-NMR analysis of the material prepared according to Preparation Example 1. Referring to FIG. 2 , it can be confirmed that the hydroxyl-terminated PDMS (PDMS-DPA) was well synthesized according to Preparation Example 1.

urethane acrylate copolymer

Example 1 (PT-PD-PT)

The three-necked round flask was washed with acetone, dried at 70 °C, and a rubber stopper and a stirrer were installed. After N ₂ purge and 30 mL of tetrahydrofuran (THF) were added dropwise, 10.00 g (12.99 mmol, 1 equivalent) of the hydroxyl group (-OH)-terminated PDMS prepared according to Preparation Example 1 was added dropwise and at 60 ° C. at 220 rpm. stirred. 0.01 g of a dibutyltin dilaurate (DBTDL) catalyst was added dropwise and stirred at 60° C. at 220 rpm for 10 minutes.

5.7740 g (25.97 mmol, 2 equivalents) of isophorone diisocyanate (IPDI) was first added dropwise, stirred at 60° C. at 220 rpm, and FT-IR was measured, and FIG. 3a shows the FT-IR result measured at this time. is shown. Referring to Figure 3a, the OH peak (3360 cm ^{- 1} ) due to the NCO bond of the OH of the PDMS and the IPID is removed, and the NH peak (3290 cm ^-1 ), C = O peak (1600) due to the urethane bond between the PDMS and the IPID cm ^{- 1} ) can be confirmed. In addition, it can be confirmed that the NCO peak (2270 cm ^{- 1} ) and the Si-O-Si peak (1024 cm ^{- 1) of PDMS by the IPID at the end were generated.}

Stir until the OH peak is removed from FT-IR (4h ~ 10h), and if the OH peak is removed, 25.97 g (25.97 mmol, 2 equivalents) of polytetramethylene ether glycol (poly(tetramethylene ether)glycol, PTMG) It was added dropwise, stirred at 60 °C at 220 rpm, and FT-IR was measured. 3b shows the FT-IR results measured at this time. Referring to FIG. 3b, it can be seen that the OH peak (3360 cm ^{- 1} ) due to the PTMG at the end is generated, and the NCO peak (2270 cm ^{- 1} ) due to the OH bond of the IPID and PTMG is removed.

Stir until the NCO peak is removed in FT-IR (4h ~ 10h), and if the NCO peak is removed, 5.7740 g (25.97 mmol, 2 equivalents) of isophorone diisocyanate (IPDI) was added dropwise a second time, and at 60 ° C. It was stirred at 220 rpm and FT-IR was measured. 3c shows the FT-IR results measured at this time. Referring to FIG 3c, OH peak due to the combination of OH and NCO IPID of PTMG ^- can be confirmed that the (3360 cm ¹⁾ is removed, and generates the NCO peak (2270 cm ^-1) due to IPID terminal.

Stir until the OH peak is removed in FT-IR (4h ~ 10h), and if the OH peak is removed, lower the RPM to 110 and the temperature to 40 ℃ hydroxyethyl methacrylate (HEMA) 3.5494 g (27.27 mmol, 2.1 eq) was diluted in 15 mL of tetrahydrofuran (THF), slowly added dropwise and stirred for 1 hour, and FT-IR was measured. 3D shows the FT-IR results measured at this time. Referring to FIG. 3d, it can be seen that the NCO peak (2270 cm ^{- 1} ) due to the combination of NCO of IPID and OH of HEMA is removed, and C=C peak (1640 cm ^{- 1} ) of HEMA is generated.

Stir until the NCO peak is removed in FT-IR (4h ~ 10h), and if the NCO peak is removed, tetrahydrofuran (THF) is removed through distillation under reduced pressure at 50 °C to remove the urethane acrylate copolymer (PT-PD- PT) was prepared.

comparative example 1 (PT-PT)

The three-necked round flask was washed with acetone, dried at 70 °C, and a rubber stopper and a stirrer were installed. After N ₂ purge and 30 mL of tetrahydrofuran (THF) was added dropwise, 34.00 g (34 mmol, 1 equivalent) of polytetramethylene ether glycol (PTMG) was added dropwise and the temperature was changed to 220 rpm at 60 ° C. stirred. 0.01 g of a dibutyltin dilaurate (DBTDL) catalyst was added dropwise and stirred at 60° C. at 220 rpm for 10 minutes.

3.7791 g (17 mmol, 0.5 equiv) of isophorone diisocyanate (IPDI) was first added dropwise, stirred at 60° C. at 220 rpm, and FT-IR was measured. 4A shows the FT-IR results measured at this time. Referring to Figure 4a, the OH peak (3360 cm ^{- 1} ) due to the PTMG at the end is generated, the NH peak (3290 cm ^{- 1} ) due to the urethane bond of PTMG and IPDI, C = O peak (1600 cm ^{- 1} ) You can see that this is created.

Stir until the NCO peak is removed in FT-IR (4h ~ 10h), and if the NCO peak is removed, 7.5582 g (34 mmol, 1 equivalent) of isophorone diisocyanate (IPDI) is added dropwise a second time, and at 60 ℃ It was stirred at 220 rpm, and FT-IR was measured. 4b shows the FT-IR results measured at this time. Referring to FIG. 4b, it can be seen that the OH peak (3360 cm ^{- 1} ) due to the NCO bond between the OH of PTMG and the IPID is removed, and the NCO peak (2270 cm ^{- 1} ) is generated due to the IPID at the end.

Stir until the OH peak (3360 cm ^{- 1} ) in FT-IR is removed (4h ~ 10h), and if the OH peak (3360 cm ^{- 1} ) is removed, lower the RPM to 110 and lower the temperature to 40 ℃ 4.8673 g (37.4 mmol, 1.1 eq) of hydroxyethyl methacrylate (HEMA) was diluted in 15 mL of tetrahydrofuran (THF), slowly added dropwise and stirred for 1 hour, and FT-IR was measured. 4c shows the FT-IR results measured at this time. Referring to FIG. 4c, it can be seen that the NCO peak (2270 cm ^{- 1} ) due to the combination of NCO of IPID and OH of HEMA is removed, and C=C peak of HEMA (1640 cm ^{- 1} ) is generated.

Stir until the NCO peak (2270 cm ^{- 1} ) in FT-IR is removed (4h ~ 10h), and if the NCO peak (2270 cm ^{- 1} ) is removed, tetrahydrofuran (THF) was added through distillation under reduced pressure at 50 ° C. was removed to prepare a urethane acrylate copolymer (PT-PT).

urethane acrylate copolymer film

Example 2 to 4 and comparative example 2 to 4

6 is a schematic view showing a method for manufacturing the urethane acrylate copolymer film of the present invention. A urethane acrylate copolymer film was prepared with reference to FIG. 6 .

Specifically, by mixing the urethane acrylate copolymer prepared according to Example 1 and Comparative Example 1, a photoinitiator (IRGARCURE 184) and a solvent (THF) in an amount according to Table 1 below, a urethane acrylate copolymer film composition was prepared prepared.

division sign Urethane acrylate copolymer (g) Photoinitiator (g) Solvent (μL) Example 2 PT-PD-PT_1wt% 4.95 0.05 60 Example 3 PT-PD-PT_3wt% 4.85 0.15 60 Example 4 PT-PD-PT_5wt% 4.75 0.25 60 Comparative Example 2 PT-PT_1wt% 4.95 0.05 60 Comparative Example 3 PT-PT_3wt% 4.85 0.15 60 Comparative Example 4 PT-PT_5wt% 4.75 0.25 60

A metal mask was placed on a glass plate, the urethane acrylate copolymer film composition was applied, and then light was irradiated to prepare a urethane acrylate copolymer film.

[Test Example]

test example One: GPC (Gel Permeation Chromatography) analysis

The urethane acrylate copolymer prepared according to Example 1 and Comparative Example 1 was subjected to GPC analysis using m-Cresol as a solvent, and the results are shown in FIG. 5 and Table 2 below.

division M _n M _w PDI Example 1 9938 20240 2.03663 Comparative Example 1 10526 19283 1.83194

test example 2: UV-Transmittance analysis

7 is a graph showing the transmittance when the film thickness prepared according to Examples 2 to 4 and Comparative Examples 2 to 4 is 500 μm, and FIG. 8 is the same graph as FIG. 7, and the wavelength ( wavelength) as a standard, it is a graph that is displayed every 30 nm.

Referring to FIGS. 7 and 8 , it can be seen that Examples 2 to 4 including the PDMS monomer in the copolymer have better light transmittance than Comparative Examples 2 to 4 not including the PDMS monomer.

test example 3: Photo DSC (Differential Scanning Calorimetry) analysis

9 shows the photo DSC analysis results of Examples 2 to 4 and Comparative Examples 2 to 4, FIG. 10a shows the photo DSC analysis results of Comparative Examples 2 to 4, and FIG. 10b is the photo DSC analysis result of Examples 2 to 4 DSC analysis results are shown. 11a shows the photo DSC analysis results of Example 2 and Comparative Example 2, FIG. 11b shows the photo DSC analysis results of Example 3 and Comparative Example 3, and FIG. 11c shows the photo DSC analysis results of Example 4 and Comparative Example 4 DSC analysis results are shown.

Using Perkin Elmer's DSC 8000 and Lumen Dynamics' Omnicure Series 2000, photo DSC analysis was performed for a total of 12 minutes by irradiating light with a wavelength of 320 to 500 nm at 25°C with an intensity of level 2 for 10 minutes. The calorific value was measured in units of time according to the light intensity. At this time, the weight of the sample is 9.5 to 10.5 mg.

Referring to FIG. 9 , it can be seen that the curing rate is lowered as the modified PDMS is added.

10a and 10b are comparisons of photo DSC photocuring rates by photoinitiator content. Referring to FIGS. 10a and 10b, it can be seen that the curing rate increases as the photoinitiator content increases, Example 2 in which the modified PDMS is added In the case of to 4, it can be seen that the curing rate is greatly affected by the content of the photoinitiator.

11a to 11c are comparisons of photo DSC photocuring rates according to the content of the modified PDMS. Referring to FIGS. 11a to 11c, when the modified PDMS is added, the curing rate is slowed, but the curing rate by adjusting the content of the photoinitiator You can see what can be adjusted.

test example 4: Check the hardness

12 is a graph showing the comparison of the pencil hardness values of Example 3 and Comparative Example 3. Although the pencil hardness of the urethane acrylate copolymer film prepared according to Example 3 and Comparative Example 3 was measured at 800 g and 20 mm/min, the pencil hardness was not measured in the coating of the entire film, so the pencil hardness was determined by whether or not the coating was peeled off. was measured. Table 3 below summarizes the pencil hardness values.

Sample Pencil Hardness Example 3 (PT-PD-PT) B Comparative Example 3 (PT-PT) 6B

12 and Table 3, it can be seen that the hardness of Example 3 including PTMG and modified PDMS inside the urethane acrylate copolymer is superior to Comparative Example 3 including only PTMG.

The scope of the present invention is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention. do.

Claims (20)

Urethane acrylate copolymer represented by the structural formula 1:
[Structural Formula 1]

In Structural Formula 1,
R ¹ is

or

ego,
R ⁴ and R ⁵ are each independently a hydrogen atom or a C1 to C5 alkyl group,
p is any one of integers from 1 to 3,
R ⁶ to R ⁸ are each independently a hydrogen atom or a C1 to C5 alkyl group,
R ² are each independently a C1 to C5 alkylene group,
R ³ is each independently a hydrogen atom or a C1 to C5 alkyl group,
n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,
n ₂ is any one of an integer from 1 to 1,000,
A is

ego,
R ⁹ is a C1 to C6 alkylene group,
q is any one of an integer from 1 to 100,
B is

ego,
R ¹⁰ is each independently a C1 to C5 alkylene group,
R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a C1 to C5 alkyl group,
r is an integer from 1 to 100. According to claim 1,
R ¹ is

or

ego,
R ⁴ and R ⁵ are each independently a hydrogen atom or a C1 to C3 alkyl group,
p is any one of integers from 1 to 3,
R ⁶ to R ⁸ are each independently a hydrogen atom or a C1 to C3 alkyl group,
R ² are each independently a C1 to C3 alkylene group,
R ³ is each independently a hydrogen atom or a C1 to C3 alkyl group,
n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,
n ₂ is any one of an integer from 1 to 1,000,
A is

ego,
R ⁹ is a C3 to C5 alkylene group,
q is any one of an integer from 1 to 100,
B is

ego,
R ¹⁰ is each independently a C2 to C4 alkylene group,
R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a C1 to C3 alkyl group,
r is an integer from 1 to 100, characterized in that the urethane acrylate copolymer. 3. The method of claim 2,
R ¹ is

or

ego,
R ⁴ and R ⁵ are each independently a hydrogen atom or a C1 to C2 alkyl group,
p is 1 or 2,
R ⁶ to R ⁸ are each independently a hydrogen atom or a C1 to C2 alkyl group,
R ² are each independently a C1 to C2 alkylene group,
R ³ is each independently a hydrogen atom or a C1 to C2 alkyl group,
n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,
n ₂ is any one of an integer from 1 to 1,000,
A is

ego,
R ⁹ is a C4 alkylene group,
q is any one of an integer from 1 to 100,
B is

ego,
R ¹⁰ is a C3 alkylene group,
R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a C1 to C2 alkyl group,
r is an integer from 1 to 100, characterized in that the urethane acrylate copolymer. 4. The method of claim 3,
R ¹ is

or

ego,
R ⁴ and R ⁵ are hydrogen atoms,
p is 1,
R ⁶ to R ⁸ are C1 alkyl groups,
R ² is a C2 alkylene group,
R ³ is a C1 alkyl group,
n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,
n ₂ is any one of an integer from 1 to 1,000,
A is

ego,
R ⁹ is a C4 alkylene group,
q is any one of an integer from 1 to 100,
B is

ego,
R ¹⁰ is a C3 alkylene group,
R ¹¹ to R ¹⁴ are C1 alkyl groups,
r is an integer from 1 to 100, characterized in that the urethane acrylate copolymer. 5. The method of claim 4,
Urethane acrylate copolymer, characterized in that the compound represented by the structural formula 1 is a compound represented by the following structural formula 2:
[Structural Formula 2]

In Structural Formula 2,
A is

ego,
q is any one of an integer from 1 to 100,
B is

ego,
r is any one of an integer from 1 to 100,
n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,
n ₂ is any one of an integer from 1 to 1,000. According to claim 1,
Urethane acrylate copolymer, characterized in that the urethane acrylate copolymer is used for 3D printing. The urethane acrylate copolymer according to claim 1; and
radical initiator;
A urethane acrylate copolymer composition comprising 8. The method of claim 7,
The urethane acrylate copolymer composition comprises 0.1 to 10 parts by weight of the radical initiator based on 100 parts by weight of the urethane acrylate copolymer. 8. The method of claim 7,
The radical initiator is 1-hydroxycyclohexyl-phenyl-ketone (1-Hydroxycyclohexyl-phenyl-ketone, IRGACURE 184), camphoquinone, ethyl-4-dimethylamino benzoate (ethyl-4-dimethylamino benzoate) , tertiary amine initiator, diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, tolylcumyliodoniumtetrakis(pentafluorophenyl)borate, acyl, Bisacyl phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide, bis( 2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one, bis(2,4,6-trimethylbenzoyl) phenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one and ethyl 2,4,6-trimethylbenzylphenyl phosphinate comprising at least one selected from the group consisting of A urethane acrylate copolymer composition comprising 8. The method of claim 7,
Urethane acrylate copolymer composition, characterized in that the urethane acrylate copolymer composition is for use in 3D printing. A molded article prepared by 3D printing and crosslinking the urethane acrylate copolymer composition according to claim 7 . (a) Compound 11 represented by Structural Formula 11 and compound 12 represented by Structural Formula 12 with an excess isocyanate group equivalent based on the hydroxyl group equivalent of Compound 11 are subjected to a urethane reaction to include compound 13 and unreacted compound 12 preparing a mixture 1 to
(b) urethane reaction of Compound 14 represented by Structural Formula 14 with an excess hydroxy group equivalent based on the isocyanate group equivalent of Compound 13 with Mixture 1 to obtain a mixture 2 comprising compound 15 and unreacted compound 14 represented by Structural Formula 15 manufacturing;
(c) urethane reaction of Compound 12 represented by Structural Formula 12 with an excess isocyanate group equivalent based on the hydroxyl group equivalent of Compound 15 with the above mixture 2 to obtain a mixture 3 comprising compound 16 and unreacted compound 12 represented by Structural Formula 16 manufacturing; and
(d) preparing a compound represented by Structural Formula 1 by urethane-reacting Compound 17 represented by Structural Formula 17 with an excess hydroxyl group equivalent based on the isocyanate group equivalent of Compound 16 with the mixture 3;
Method for producing a urethane acrylate copolymer comprising:
[Scheme 1]

In Scheme 1,
R ¹ is

or

ego,
R ⁴ and R ⁵ are each independently a hydrogen atom or a C1 to C5 alkyl group,
p is any one of integers from 1 to 3,
R ⁶ to R ⁸ are each independently a hydrogen atom or a C1 to C5 alkyl group,
R ² are each independently a C1 to C5 alkylene group,
R ³ is each independently a hydrogen atom or a C1 to C5 alkyl group,
n ₁ and n ₃ are each independently any one of an integer from 1 to 1,000,
n ₂ is any one of an integer from 1 to 1,000,
A is

ego,
R ⁹ is a C1 to C6 alkylene group,
q is any one of an integer from 1 to 100,
B is

ego,
R ¹⁰ is each independently a C1 to C5 alkylene group,
R ¹¹ to R ¹⁴ are each independently a hydrogen atom or a C1 to C5 alkyl group,
r is an integer from 1 to 100. 13. The method of claim 12,
Preparation of a urethane acrylate copolymer wherein step (a) comprises 101 to 300 equivalents of the isocyanate group of the compound 12 represented by the structural formula 12 based on 100 equivalents of the hydroxyl group of the compound 11 represented by the structural formula 11 Way. 13. The method of claim 12,
Preparation of a urethane acrylate copolymer, characterized in that the step (b) comprises 101 to 300 equivalents of the hydroxyl group of the compound 14 represented by the structural formula 14 based on 100 equivalents of the isocyanate group of the compound 13 represented by the structural formula 13 Way. 13. The method of claim 12,
Preparation of a urethane acrylate copolymer wherein step (c) comprises 101 to 300 equivalents of the isocyanate group of the compound 12 represented by the structural formula 12 based on 100 equivalents of the hydroxyl group of the compound 15 represented by the structural formula 15 Way. 13. The method of claim 12,
Preparation of a urethane acrylate copolymer wherein step (d) comprises 101 to 300 equivalents of the hydroxyl group of the compound 17 represented by the structural formula 17 based on 100 equivalents of the isocyanate group of the compound 16 represented by the structural formula 16 Way. 13. The method of claim 12,
Method for producing a urethane acrylate copolymer, characterized in that the reaction of steps (a) to (d) uses dibutyltin dilaurate (DBTDL) as a catalyst. 13. The method of claim 12,
The reactions of steps (a) to (c) are each independently carried out at a temperature of 30 to 100 °C,
Method for producing a urethane acrylate copolymer, characterized in that the reaction of step (d) is carried out at a temperature of 30 to 45 ℃. 13. The method of claim 12,
Method for producing a urethane acrylate copolymer, characterized in that the reaction of steps (a) to (d) is carried out by solution polymerization using a solvent. 20. The method of claim 19,
Preparation of urethane acrylate copolymer, characterized in that the solvent comprises at least one selected from the group consisting of tetrahydrofuran (THF), toluene, dimethylformamide (DMF) and acetone (Acetone) Way.

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