KR20190011963A - A method for evaluating a solvent in coating a film including an organic dye - Google Patents

Abstract

The present invention relates to a method for evaluating characteristics of film coating solvent including organic dye, the method including: (i) obtaining mixed energy (E_(solvent-binder)) between a main solvent and an auxiliary solvent and a polymer binder to determine the commercial use of solvents in the range of a candidate group for a main solvent and an auxiliary solvent; (ii) calculating a Hansen solubility parameters distance (dist_(solvent-main solvent)) between the auxiliary solvents and the main solvent to determine the affinity between the auxiliary solvents and the main solvent; (iii) obtaining molecular weights of the main solvent and the auxiliary solvents to consider the mobility of the main solvent and the auxiliary solvents; and evaluating characteristics of the coating solvent by calculating a score (SOF-Score) for each solvent by using values obtained by performing the above steps (i) to (iii). Accordingly, the characteristics of the film-coating solvent are effectively evaluated, and the auxiliary solvent is effectively selected.

Description

[0001] The present invention relates to a method for evaluating the properties of a film-coating solvent containing an organic dye,

The present invention relates to a method for evaluating the properties of film-coating solvents containing organic dyes, and more particularly, to evaluating the characteristics of a co-solvent by introducing parameters in evaluating the characteristics of the co- ≪ / RTI >

It has been reported that the life time of the organic fluorescent material used for the fluorescent film is shortened due to photobleaching phenomenon. The light discoloration phenomenon is a phenomenon in which a fluorescent dye absorbs energy, emits light, and returns to the ground state. As a result, a new covalent bond is formed in the material and the structure is destroyed, Phenomenon. In order to prevent the above phenomenon, it is important to minimize the contact of the fluorescent material with oxygen or water using a polymer binder. In order to avoid contact with oxygen and moisture, the structure of the polymer binder in the coating liquid must be widely spread when the film is made, and the residual solvent should be minimized in the produced film. For this purpose, the mobility of the solvent molecules should be high. The above is described in the non-patent prior art Wong et al , Polymer , 2004, 45, 5151 and Schabel et al , Chem. Eng. Sci., 2007, 62, 2254.

In order to minimize the residue of the coating solvent, it can be solved by adding a co-solvent to the main solvent. In order to select the co-solvent, a method of evaluating the characteristics of the coating solvent in consideration of compatibility with the polymer binder is necessary.

A method for evaluating the properties of a film coating solvent comprising an organic dye of the present invention comprises:

(i) mixing _solvent ( E _{solvent-binder} ) between the main solvent and each of the auxiliary solvents and the polymer binder to determine the compatibility of the solvent with respect to each of the main solvent and the solvent belonging to the candidate solvent of the auxiliary solvent ;

(ii) a Hansen solubility parameters distance ( dist _{solvent-main solvent} ) between the respective auxiliary solvents and the main solvent to determine affinity between the respective auxiliary solvents and the _{main solvent} );

(iii) obtaining the molecular weights ( M _w ) of the main solvent and the respective auxiliary solvents in order to consider the mobility of the main solvent and the auxiliary solvents; And

(iv) by substituting each of Equation 1 the values obtained by performing each of the (i) - (iii) steps with respect to the main solvent and a co-solvent solvent belonging to the candidate score for each of the solvents (SOF -Score ) to evaluate the characteristics of the coating solvent,

[Equation 1]

Max.M _w is the molecular weight of the solvent having the largest molecular weight among the solvents belonging to the main solvent and the candidate solvent group, and Min. E _{solvent -binder} is E _solvent for the solvent belonging to the group consisting of the primary solvent and the cosolvent candidates _- may be a value the smallest of the values _binder.

Further, in the method for evaluating the characteristics of the film coating solvent containing the organic dye of the present invention, it is preferable that, prior to the step (i), the step of selecting solvents as a candidate for an auxiliary solvent includes the steps of: May be selected as the candidate for the auxiliary solvent.

Further, in the method for evaluating the characteristics of the film coating solvent containing the organic dye of the present invention, in the step of selecting the solvents as the candidate for the auxiliary solvent, steps (i) to (iii) are carried out even if the boiling point is lower than the boiling point of the main solvent. ) in the case where expected to be obtained in a favorable SOF -Score, it may be selected as the co-solvent candidate.

Further, in the method for evaluating the characteristics of the film coating solvent containing the organic dye of the present invention, among the scores ( SOF- Score ) for the auxiliary solvents calculated in the step (iv) As a co-solvent for the film-coating solvent.

Further, in the method for evaluating the properties of the film coating solvent containing an organic dye of the present invention, the main solvent, and mixing energy (E _{solvent -binder)} with said each of the co-solvent and a polymeric binder (binder) is COSMO-RS ( conductor-like screening model for real solvent.

Further, in the method of evaluating the characteristics of the film coating solvent containing the organic dye of the present invention, the Hansen solubility parameter distance ( dist _{solvent-main solvent} ) of each of the above-mentioned auxiliary solvents and the main solvent is calculated by applying Lt; / RTI >

&Quot; (4) "

,

,

and δD _solvent and δD _{main solvent} are Hansen solubility parameters (Hansen solubility parameters for dispersion) value related to the variance of each of the co-solvent and primary solvent, δP _solvent and δP _{main solvent} are Hansen relates to a polar covalent bond, each co-solvent and primary solvent And the? H _solvent and? H _{main solvent} may be Hansen solubility parameters for hydrogen bonding values for the hydrogen bonding of the co-solvent and the _{main solvent} , respectively.

In the method for evaluating the characteristics of a film coating solvent containing an organic dye according to the present invention, the organic dye may be any one or more selected from the group consisting of fluorescein, tetramethylrhodamine (TMR), naphthofluorescein, propidium, Lucifer Yellow and resorufin .

In the method for evaluating the characteristics of the film-coating solvent containing the organic dye of the present invention, the main solvent is benzyl acetate, ethyl acetate, dimethyl formamide, n, n-dimethyl acetamide, pyridine, n, And the auxiliary solvent is selected from the group consisting of propyl acetate, n-dimethyl acetamide, pyridine, n-vinylpyrrolidone, 3-methyl-2-oxazolidone, pyrrolidinone, 1-methylindole, benzonitrile, 1-methoxynaphthalene, phenyl acetate, and butyl acetate.

In addition, in the method of evaluating the characteristics of the film coating solvent containing the organic dye of the present invention, the polymeric binder may be selected from styrene-acrylonitrile resin (SAN), ethylene vinyl acetate (EVA), polyethylene (PE) , Polypropylene (PP), polystyrene (PS), and polymethyl methacrylate (PMMA).

The development of SOF- Score capable of scoring solvent characteristics by using parameters when selecting coating solvents for films containing organic dyes can effectively evaluate the characteristics of film-coating solvents containing organic dyes, Can be effectively screened.

1 is a diagram showing the Hansen solubility parameter of the auxiliary solvent candidate group.
FIG. 2 is a diagram showing the selection of an auxiliary solvent by indicating the solvent candidate group characteristics with a score. FIG.

According to the method for evaluating the characteristics of the auxiliary solvent of the coating film containing the organic dye according to the present invention, each solvent is scored and priorities are determined. The scoring conditions of the solvent according to the present invention are as follows.

(Condition 1) The co-solvent should remain until the end of drying in order to increase the mobility of the main solvent. The boiling point of the co-solvent may be as high as or higher than the main solvent. However, even if the boiling point is lower than the main solvent, it can belong to the candidate group when it is expected that favorable SOF- Score can be obtained by applying the following conditions 2, 3 and 4. If the boiling point is too high, It can be overdosed, so it can be excluded from the candidate group.

(Condition 2) The solubility of the polymer binder and the solvent should be high. To determine the compatibility of the solvent in the group consisting of the main solvent and at least one auxiliary solvent belonging to the candidate group of the auxiliary solvent, the mixing energy of the polymer binder and the solvent is calculated do.

(Condition 3) To determine the affinity between the co-solvent and the main solvent, the Hansen solubility parameters of the co-solvent and the main solvent are analyzed.

(Condition 4) The molecular weight of the solvent is considered to increase the mobility of the solvent.

According to the invention, through the SOF -Score (Score of Solvents for Organic Film) that can be scored by applying the above conditions, and to evaluate the solvent properties may be screened for the co-solvent suitable therefore.

The organic dye is an organic substance containing a fluorescent substance, for example, one or more of BODIPY-FLBODIPY-TR, IrDye 700DX (trade name), fluorescein, TMR (tetramethylrhodamine), naphthofluorescein, propidium, Lucifer Yellow and resorufin .

The main solvent may be selected from the group consisting of, for example, benzyl acetate, butyl acetate, ethyl acetate, dimethyl formamide, n, n-dimethyl acetamide, pyridine, n, 1-ethyl-2-pyrrolidinone, 1-methylindole, benzonitrile, 1-methoxynaphthalene, phenyl acetate, butyl acetate ≪ / RTI > Examples of the polymer binder include styrene-acrylonitrile resin (SAN), ethylene vinyl acetate (EVA), polyethylene (PE), polypropylene (PP), polystyrene (PS) and polymethyl methacrylate ) May be used.

Hereinafter, a method of scoring according to a solvent for evaluating solvent characteristics of a coating film containing an organic dye according to the present invention will be described in detail.

First, the candidate group of the auxiliary solvent is selected. The co-solvent should remain until the end of drying in order to increase the mobility of the main solvent, while the residual amount of the co-solvent or main solvent in the finally produced organic fluorescent film should be minimized. For this purpose, the co-solvent should remain until the end of drying in order to increase the mobility of the main solvent, and the boiling point may be as good as or higher than the main solvent. However, even if the boiling point is lower than the main solvent, it can belong to the candidate group if SOF- Score favorable in the condition 2, 3 or 4 is obtained. If the boiling point is too high, the residual solvent amount may be higher than the main solvent Rather, candidates can be excluded.

Further, according to the present invention, the SOF - Score (Score of Solvents for Organic Film) represented by the following formula (1) is calculated for the group consisting of the main solvent and the auxiliary solvents selected as the candidate group, do.

[Equation 1]

In the above equation 1, M _w is the molecular weight of the candidate solvent material, E is a mixed _{solvent -binder} energy (mixing energy) (kcal / mol ) of a polymeric binder and a solvent, _{solvent-dist main solvent} is the main solvent and the auxiliary And the Hansen solubility parameters distance of the solvent. Also, Max.M _w is a molecular weight value of the largest molecular weight material in the solvent material belonging to the group consisting of a primary solvent and a secondary solvent candidate. Also, Min. E _{solvent -binder} is the smallest value among the E _{solvent-binder} values for each of the solvent materials belonging to the group consisting of the main solvent and the auxiliary solvent group.

M _{w, which} is the molecular weight of the main solvent and the candidate co-solvent, can be referenced, for example, in Table 1 below.

Candidate solvent substance Molecular weight ( M _w ) dimethylformamide 73.1 n, n-dimethyl acetamide 87.1 propyl acetate 102.13 benzo nitrile 103.1 butyl acetate 116.16 phenyl acetate 136.15 1-methoxynaphthalene 158.2

In addition, E _{solvent- binder, which} is the energy of mixing of polymer binder and solvent, can be calculated by applying the theory of COSMO-RS (conductor _cleaning model for real solvent). Mixing energy of E _{-binder solvent} of the polymer binder and the solvent may contain derived with the COSMO-RS COSMOtherm related program, for example. Mixing energy value of E _{solvent -binder} of an exemplary polymer binder and solvents, see the EXAMPLES which will be described later.

C ₁ is an adjustment coefficient in the range of 0.1 to 10 which is adjusted depending on the type of the binder, and can be applied, for example, as shown in Table 2 below. C ₂ is an adjustment factor between 0.1 and 10, which is adjusted according to the main solvent. For example, it can be applied as shown in Table 3 below.

bookbinder Adjustment factor ( C ₁ ) Styrene acrylonitrile resin (SAN) One

Main solvent Adjustment factor ( C ₂ ) Butyl acetate One dimethylformamide One

Meanwhile, the Hansen solubility parameter distance is one of the methods for evaluating the similarity of two materials. The dispersion parameter of the material, the polar-bonding parameter, the hydrogen-bonding ) ≪ / RTI > parameter into the following equation (2), the value can be derived by the following equation (3) written as Ra .

&Quot; (2) "

&Quot; (3) "

Where δD _i is the Hansen solubility parameters for dispersion value for the dispersion of material i, δP _i is the Hansen solubility parameters for polar-bonding for the polar covalent bond of material i, δH _i is the Hansen solubility parameters for hydrogen-bonding values for the hydrogen bond of material i. In addition, the value of Hansen solubility parameter of dispersion in δD _i, the value of Hansen solubility parameters in Hansen solubility parameter δP value of _i, and hydrogen bonding of the polar covalent δH _i is, For example, by the Hansen Solubility Parameter in Practice (HSPiP) program.

Accordingly, in the above formula (1), dist _{solvent- major solvent, which} is the Hansen solubility parameter distance between the main solvent and the auxiliary solvent, can be expressed by the following equation (4).

&Quot; (4) "

1, for example, the Hansen solubility parameter values δD, δP, and δP in the case where the main solvent is dimethylformamide and the auxiliary solvent is n, n-dimethylacetamid, propylacetate, benzonitrile, butylacetate, phenylacetate and 1-methoxynaphthalene , < / RTI > In FIG. 1, the difference in 隆 D, 隆 P, and 隆 H values with respect to the main solvent in the case of n, n-dimethylacetamide, which is the co-solvent 1, is the smallest, and dist _{solvent -main solvent} value is also smallest.

On the other hand, in the above equation 1, since the smaller the value E _{solvent -binder} cosolvent is good compatibility with the binder polymer, the smaller the value of dist _{solvent -main solvent} means that the co-solvent is similar to that of the main solvent, SOF - The smaller the score , the better the screening performance of the auxiliary solvent can be expected.

[Example]

The following examples are the results of evaluating the characteristics of the coating solvent in order to select an auxiliary solvent that minimizes the residual amount of the main solvent when preparing the color conversion film for LCD. The embodiments of the present invention described below are only examples, and the scope of the present invention is not limited to these embodiments. It is intended that the scope of the invention be indicated by the appended claims and include all changes that come within the meaning and range of equivalency of the claims which follow.

In one embodiment, when the main solvent of the color conversion film for LCD is dimethylformamide, the characteristics of the coating solvent may be evaluated as follows when the auxiliary solvent for minimizing the residual solvent is selected.

(Step 1) The boiling point of dimethylformamide, which is the main solvent, is 153 ° C., and the candidate group is selected from the auxiliary solvents having a boiling point equal to or higher than the boiling point. However, even if the boiling point is lower than the main solvent, it can belong to the candidate group when it is expected that the advantageous SOF- Score can be obtained in the following steps 2 to 4. For example, the boiling points of n, n-dimethylacetamid, propylacetate, benzonitrile, butylacetate, phenylacetate and 1-methoxynaphthalene are 166, 101.3, 190, 126.1, 196 and 136 ° C, respectively. Subsequently, the auxiliary solvents 1 to 6 are selected as the auxiliary solvent candidates.

(Step 2) _{Calculate the} mixing energy ( E _{solvent- binder} ) by applying the COSMO-RS theory as a measure of the solubility of the main solvent and the candidate solvent candidate selected in Step 1 and the polymer binder SAN being used. For example, the mixing energy of the polymeric binder SAN and the main solvent 1 dimethylacetamide can be derived by applying the COSMOtherm program according to the COSMO-RS theory, where the _{solvent- binder} value of the mixed energy E is -3.72 kcal / mol). Likewise, when the mixing energy is derived for the auxiliary solvents 1 to 6 in the same manner, the values are -3.50, -1.73, -0.78, -1.13, -1.82, and -0.76 (kcal / mol), respectively. Also, Min. E _{solvent -binder} is the lowest value among the seven E _{solvent- binder} values of -3.72 (kcal / mol).

(Step 3) The Hanse solubility parameter is analyzed to determine the affinity between the candidate solvent candidate and the main solvent selected in step 1. For example, the Hansen solubility parameters, which are values of the main solvent dimethylformamide _{main solvent} δD, δP _{main solvent,} δH _{main solvent} are respectively 17.4, 13.7, 11.3. In addition, the co-solvent is n 1, Hansen solubility parameter values, which are _solvent1 δD, δP _solvent1, δH _solvent1 of n-dimethylacetamide are respectively 16.8, 11.5, 9.4. For reference, FIG. 1 shows the Hansen solubility parameter values of the main solvent and the auxiliary solvents 1 to 6. ΔD which are Hansen solubility parameter values of the main solvent _{main solvent,} δP _{main solvent,} δH _main When the _solvent and co-solvent 1 Hansen, which are the solubility parameters δD _solvent1, δP _solvent1, δH _solvent1 of substituted into Equation 4, dist _{solvent1-main solvent} Value can be derived.

(Step 4) The molecular weight ( M _w ) of the solvent is taken into consideration, since the residual solvent of the organic fluorescent film is minimized when the mobility of the solvent is high. For example, the molecular weights of the main solvent and the co-solvents 1 to 6 are 73.1, 87.1, 102.13, 103.1, 116.16, 136.15 and 158.2, respectively. Also, Max.M _w is the maximum value of 158.2 in place of 7 molecular weight values.

(Step 5) In Step 1, SOF- Score is calculated for each of the auxiliary solvents 1 to 6 selected as the auxiliary solvent candidates, and the auxiliary solvent characteristics are scored. Specifically, the values derived in steps 2 to 4 are substituted into equation (1), and SOF- Score is calculated for each of the co-solvents 1 to 6, and the scores are 0.89, 2.31, 2.37, 2.80, 3.05, 3.90 to be. Note that, in Fig. 2 shows the rating of SOF -Score for the co-solvent from 1 to 6 as a graph. Then, of the SOF- Scores calculated for each of the co-solvents 1 to 6, the n-dimethylacetamide substance 1, which is the lowest-scoring co-solvent, is finally selected as an auxiliary solvent for the film coating solvent containing the organic dye can do.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. In addition, the scope of the present invention is indicated by the following claims rather than the above detailed description. Also, all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (9)

A method for evaluating the properties of a film-coating solvent comprising an organic dye comprising:
(i) a main solvent and the primary solvent and the mixing energy (E _{solvent -binder)} with each of the co-solvent and a polymeric binder (binder) in order to determine the compatibility of a solvent for each of the solvent belonging to the candidate co-solvent ;
(ii) a Hansen solubility parameters distance ( dist _{solvent-main solvent} ) between the respective auxiliary solvents and the main solvent to determine affinity between the respective auxiliary solvents and the _{main solvent} );
(iii) obtaining the molecular weights ( M _w ) of the main solvent and the respective auxiliary solvents in order to consider the mobility of the main solvent and the auxiliary solvents; And
(iv) by substituting each of Equation 1 the values obtained by performing each of the (i) - (iii) steps with respect to the main solvent and a co-solvent solvent belonging to the candidate score for each of the solvents (SOF -Score ) to evaluate the characteristics of the coating solvent,
[Equation 1]

Max.M _w is the molecular weight of the solvent having the largest molecular weight among the solvents belonging to the main solvent and the candidate solvent group, and Min. E _{solvent -binder} is E _solvent for the solvent belonging to the group consisting of the primary solvent and the cosolvent _{candidate-way} evaluation _binder smallest value, among the values coating solvent properties. The method according to claim 1,
The method according to any one of the preceding claims, further comprising, prior to step (i), selecting solvents as candidate co-solvent candidates, further comprising selecting solvents having a boiling point equal to or higher than the boiling point of the main solvent Assessment Methods. 3. The method of claim 2,
When it is expected that SOF- Score favorable in steps (i) to (iii) can be obtained even if the boiling point is lower than the boiling point of the main solvent in the step of selecting solvents as the auxiliary solvent candidate, A method for evaluating characteristics of a coating solvent capable of being selected. The method according to claim 1,
And selecting an auxiliary solvent having a smallest value among the scores ( SOF- Score ) for the auxiliary solvents calculated in the step (iv) as an auxiliary solvent for the film-coating solvent. Assessment Methods. The method according to claim 1,
Wherein a mixing energy ( E _solvent- binder) between the main solvent and each of the auxiliary solvents and the polymer binder is obtained by applying a conductor screening model for real solvent (COSMO-RS). The method according to claim 1,
The Hansen solubility parameter distance ( dist _{solvent-main solvent} ) of each of the auxiliary solvents and the _{main solvent} can be derived by applying Equation (4)
&Quot; (4) "

,
and δD _solvent and δD _{main solvent} are Hansen solubility parameters (Hansen solubility parameters for dispersion) value related to the variance of each of the co-solvent and primary solvent, δP _solvent and δP _{main solvent} are Hansen relates to a polar covalent bond, each co-solvent and primary solvent solubility parameters (Hansen solubility parameters for polar-bonding ) value and, δH _solvent and δH _{main solvent} are Hansen solubility parameters (Hansen solubility parameters for hydrogen-bonding ) value, the coating solvent properties for the hydrogen bonding of each of the co-solvent and primary solvent evaluation Way. The method according to claim 1,
Wherein the organic dye is at least one selected from the group consisting of fluorescein, tetramethylrhodamine (TMR), naphthofluorescein, propidium, Lucifer Yellow and resorufin. The method according to claim 1,
Wherein the main solvent is any one selected from the group consisting of benzyl acetate, butyl acetate, ethyl acetate, dimethyl formamide, n, n-dimethyl acetamide, pyridine, n, 1-methyl-2-pyrrolidinone, 1-methylindole, benzonitrile, 1-methoxynaphthalene, phenyl acetate, butyl acetate , Wherein the coating solvent is a solvent. The method according to claim 1,
The polymeric binder may be selected from the group consisting of styrene-acrylonitrile resin (SAN), ethylene vinyl acetate (EVA), polyethylene (PE), polypropylene (PP), polystyrene (PS) and polymethylmethacrylate , And a copolymer of said copolymer and said copolymer.

Images