JPH0694594A - Evaluation method for resin surface characteristic - Google Patents

Abstract

PURPOSE:To evaluate the surface characteristics of a resin including thermal characteristics by measuring a dynamic contact angle with variation of the temperature of liquid including water and organic solvent. CONSTITUTION:Resin to be evaluated is hung down from a load detector 12a and liquid is poured in a liquid container 14. Water or an organic solvent is controlled at a specified temperature with a circulation temperature controller 1. Then, a driver part 15 is operated to move up the container 14 and the load of throwing the resin 13 in the container 14 is detected with a load detector 12a and the contact angle (forward angle) is indicated on a contact angle indicator 12b. By operating the driver part 15, the resin 13 is pulled out of the container 14 and the load of pulling up is detected with the detector 12 and the contact angle backward angle) is indicated on the contact angle indicator 12b. Then, the liquid temperature in the container 14 is varied with the controlled to a specified temperature, and by repeating the similar operation for desired times, dynamic contact angle of the resin 13 related to thermal variations can be measured. Also, by varying the liquid temperature continuously and repeating the similar operation, dynamic contact angle of the resin can be measured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel evaluation method for evaluating surface characteristics such as water repellency and oil repellency of a resin which is measured in determining a practical application range of the resin.

[0002]

2. Description of the Related Art Conventionally, various resin materials have been developed and widely used in various fields with the progress of the field of organic chemistry.
Various methods for evaluating the properties of such resins have been proposed and implemented, but among them, their surface properties have a great influence on the practical performance of the resins.

As a method for evaluating the surface characteristics of such a resin, for example, a Fourier transform infrared spectrometer (FT-I) is used.
R), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (S
A spectroscopic method using EM) and the like; a physical method for measuring adhesion, tackiness, peeling phenomenon and the like, a contact angle measuring method and the like are known. In particular, it is known that the contact angle measuring method can directly evaluate the surface characteristics of the resin in practical use. As the contact angle measuring method, a static contact angle measuring method for measuring a liquid droplet on a stationary resin and a supporting plate coated with a resin or a resin in a liquid are moved up and down to measure a tension related to a resin surface, There is a dynamic contact angle measuring method for evaluating the surface characteristics of a resin, and the dynamic contact angle measuring method is particularly excellent in reproducibility.

However, in the above-mentioned conventional contact angle measuring method, the measurement was performed only at room temperature, and no consideration was made on the temperature dependence of the contact angle, that is, the relationship between the surface characteristics and the thermal characteristics. However, in the current situation, the desired surface property evaluation has not been carried out in the case of a resin which is particularly apt to change due to a thermal action, and further a resin which is used at a high temperature.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel resin surface property evaluation method capable of directly evaluating surface properties such as water repellency and oil repellency of a resin including thermal properties. To provide.

[0006]

According to the present invention, when the surface characteristics of a resin are evaluated by dynamic contact angle measurement, the dynamic contact angle measurement is performed on a liquid containing water and / or an organic solvent. A method for evaluating resin surface characteristics is provided, which is characterized in that the temperature of the liquid is changed and measured.

The present invention will be described in more detail below.

In the evaluation method of the present invention, the resin to be measured is not particularly limited, and poly (isopropyl fumarate-3,3,4,5,5,6,6,6) is used.
7,7,8,8,8-tridecafluorooctyl), poly (isopropyl fumarate-3,3,4,4,5,5,5)
6,6,7,7,8,8,9,9,10,10,10-
Heptadecafluorodecyl) and other polyfumaric acid esters, poly (meth) acrylic acid esters, polyitaconic acid esters, triacetyl cellulose, polyethylene terephthalate, polystyrene resins, polyolefin resins, polyester resins, polyurethane resins, etc. For example, a resin molded in a plate shape; a resin coated on an inorganic substrate such as glass or a silicon wafer or a polymer substrate such as vinyl chloride or polyethylene terephthalate; a film-forming resin attached to these substrates It can be used for measurement according to the above.

In the evaluation method of the present invention, the resin to be evaluated can be molded into the above-mentioned form and the like, and can be measured in a liquid containing water and / or an organic solvent according to a usual dynamic contact angle measuring method. At this time, it is necessary to measure by changing the temperature of the liquid. By thus measuring the temperature of the liquid while changing it, it is possible to clearly evaluate the surface characteristics of the resin related to the thermal characteristics.

As the liquid used in the present invention, a liquid which does not dissolve the resin to be evaluated and preferably has a sufficiently high boiling point with respect to the temperature range in which the temperature is changed may be appropriately selected, for example, water or an organic solvent. As n-dodecane, n
-Decane, n-undecane, hexane, octane, a commercially available standard solution of wetting index, and the like, and an emulsion or suspension containing these can be given.

The temperature range for changing the temperature of the liquid can be appropriately determined depending on the resin to be evaluated and the purpose, for example, practically -20 to 120 ° C., preferably surface characteristics of the resin. In the temperature range in which the thermal requirements are likely to affect, for example, the temperature around the molecular motion of the resin to be evaluated, especially the glass transition temperature of the resin to be evaluated, and further the glass transition temperature of the resin to be evaluated ± 3
It is desirable to change the temperature at 0 ° C., particularly within the temperature range of the glass transition temperature of the resin to be evaluated ± 20 ° C. At this time, the temperature to be changed may be continuous change or stepwise change. Preferably, when the resin to be evaluated is the same, the temperature is continuously changed and the resin to be evaluated is changed. When a plurality of different objects are used, it is desirable to change the temperature stepwise for measurement.

As a device that can be used for carrying out the evaluation method of the present invention, in a commercially available dynamic contact angle measuring device or the like, it is possible to adjust the temperature of the liquid into which the sample to be evaluated is added to a predetermined temperature. There is no particular limitation as long as it is an apparatus including a liquid temperature controller that can be used.

Further, in the evaluation method of the present invention, in order to further clarify the relationship between the surface characteristics and the thermal characteristics, it is preferable to measure two or more kinds of water and an organic solvent for the resin to be evaluated. Specifically, for example, water is used to measure the temperature dependence of the molecular motion of hydrophilic or water-repellent groups in the resin, while the temperature dependence of the molecular motion of lipophilic or oil-repellent groups in the resin is used. In order to measure the property, it is preferable to analyze using an organic solvent, and when investigating the temperature dependence of these two molecular motions, it is preferable to measure separately for both water and the organic solvent.

It is also possible to measure with a liquid suitable for practical use. Specifically, for example, for a resin used for coating the ink ejecting portion of a printer, the dynamic contact angle with respect to ink is For the resin used to coat the surface of the biocompatible material, the temperature characteristic of liquid repellency under each practical condition can be evaluated by measuring the dynamic contact angle with respect to blood components, etc. .

Specifically, one embodiment of the apparatus and an example of the evaluation method of the present invention will be specifically described with reference to FIG. 1, but the present invention is not limited to this.

In FIG. 1, 10 is a dynamic contact angle measuring device equipped with a circulation type temperature controller 11 which can be used in the evaluation method of the present invention. The dynamic contact angle measuring device 10 includes a load detector 12 for detecting a load change of a resin 13 as a measurement sample.
a, a contact angle display unit 12b that converts the load detected by the load detection unit 12a into a contact angle and displays the contact angle, and a liquid storage unit 14 that stores a liquid and is connected to the circulation temperature controller 11.
And a drive unit 15 for moving the liquid storage unit 14 up and down so that the resin 13 can move up and down in the liquid storage unit 14.

In the evaluation method of the present invention, the resin 13 to be evaluated is used.
Is hung on the load detection unit 12a, an appropriate liquid is put into the liquid storage unit 14, and the circulating temperature controller 11 adjusts the water or the organic solvent to a predetermined temperature.
Is operated to move the liquid storage portion 14 upward, and the load when the resin 13 is put into the liquid storage portion 14 is detected by the load detection portion 12a, and the contact angle (forward movement) is displayed on the contact angle display portion 12b. (Corner) is displayed. Next, the drive unit 15 is operated to move the liquid storage unit 14 downward, so that the resin 13
Is lifted from inside the liquid storage portion 14, and the load at the time of lifting is detected by the load detection portion 12a, and the contact angle display portion 1
The contact angle (receding angle) is displayed on 2b. Then, the temperature of the liquid in the liquid storage unit 14 is changed by the circulation type temperature controller 11, and when the temperature reaches a predetermined temperature, the same operation as described above is repeated a desired number of times, thereby dynamically changing the temperature of the resin 13. The contact angle can be measured. Further, the dynamic contact angle of the resin 13 can be measured by repeating the same operation as described above while continuously changing the temperature of the liquid in the liquid storage portion 14 by the circulation type temperature controller 11.

[0018]

In the evaluation method of the present invention, a liquid containing water and / or an organic solvent is used, and the dynamic contact angle is measured by changing the temperature of the liquid. , Surface characteristics such as heat resistance, weather resistance and curable substrate adhesion and thermal characteristics can be clarified, and surface characteristics of the resin in a practical temperature range can be evaluated.

[0019]

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

[0020]

Example 1 As a resin, poly (isopropyl fumarate-3,3,4,4,5,5,6,6,7,7,8,8,
8-tridecafluorooctyl) (glass transition temperature 25
C.), 1,1,2-trichloro-1,
A 1% by weight solution of 2,2-trifluoroethane was prepared.
Then, a 20 × 50 × 0.5 mm vinyl chloride substrate was immersed in the resin solution to prepare a resin-coated substrate, which was used as a sample substrate. The obtained sample substrate was placed in place of the resin 13 of the dynamic contact angle measuring device 10 shown in FIG. 1 described above, and the same method was used for pure water at a measurement temperature of 5 to 50 ° C. at every 5 ° C. And the dynamic contact angles of the advancing angle and the receding angle were measured. The result is shown in FIG. From the results of FIG. 2, it was confirmed that the receding angle was decreased and the water repellency of the resin was decreased at the glass transition temperature or higher.

[0021]

Example 2 The dynamic contact angle was measured in the same manner as in Example 1 except that n-dodecane was used instead of pure water. The result is shown in FIG. From the results of FIG. 3, it was confirmed that the advancing angle and the receding angle both increased at the glass transition temperature or higher, and the oil repellency of the resin increased.

[0022]

Example 3 As resin, poly (isopropyl fumarate-3,3,4,4,5,5,6,6,7,7,8,8,
Example 1 except that 9,9,10,10,10-heptadecafluorodecyl) (glass transition temperature 32 ° C.) was used.
The dynamic contact angle was measured in the same manner as above. The result is shown in FIG. From the results of FIG. 4, it was confirmed that the receding angle was decreased and the water repellency of the resin was decreased at the glass transition temperature or higher.

[0023]

Example 4 The dynamic contact angle was measured in the same manner as in Example 3 except that n-dodecane was used instead of pure water. The result is shown in FIG. From the results of FIG. 5, it was confirmed that the advancing angle and the receding angle both increased at the glass transition temperature or higher, and the oil repellency of the resin increased.

[0024]

Example 5 The same as Example 1 except that a 20 × 50 × 0.16 mm plate-like film of triacetyl cellulose (glass transition temperature 43 ° C.) was used as the resin and the measurement temperature was 20 to 60 ° C. Then, the dynamic contact angle was measured. The result is shown in FIG. From the results of FIG. 6, it was confirmed that the receding angle was decreased and the water repellency of the resin was decreased at the glass transition temperature or higher.

[0025]

Example 6 As a resin, polyethylene terephthalate (glass transition temperature 73 ° C.) 20 × 50 × 0.10 mm
The dynamic contact angle was measured in the same manner as in Example 1 except that the plate-shaped film of 1 was used and the measurement temperature was 50 to 90 ° C.
The result is shown in FIG. 7. From the results shown in FIG. 7, no change in contact angle was observed near the glass transition temperature, and it was found that the resin having no side chain such as polyethylene terephthalate has no temperature dependence of water repellency.

[0026]

Example 7 As a resin, isopropyl fumarate-3,
3,4,4,5,5,6,6,7,7,8,8,9,
Copolymer of 9,10,10,10-heptadecafluorodecyl) and vinyl ethylmethylbutanoate (composition weight ratio =
8: 2; glass transition temperature 40 ° C.), 20 × 50 × 0.
The dynamic contact angle was measured in the same manner as in Example 1 except that a 1 mm commercially available cover glass was used and a bottle ink manufactured by Ecole was used instead of pure water. The result is shown in FIG. From the results of FIG. 8, it was confirmed that the receding angle was decreased at the glass transition temperature or higher, and the liquid repellency of the resin to ink was decreased.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a dynamic contact angle measuring device that can be used in the evaluation method of the present invention.

FIG. 2 is a graph showing the results of the dynamic contact angle of the resin surface with respect to the temperature change measured in Example 1.

FIG. 3 is a graph showing the results of the dynamic contact angle of the resin surface with respect to the temperature change measured in Example 2.

FIG. 4 is a graph showing the results of the dynamic contact angle of the resin surface with respect to the temperature change measured in Example 3.

FIG. 5 is a graph showing the results of the dynamic contact angle of the resin surface with respect to the temperature change measured in Example 4.

FIG. 6 is a graph showing the results of the dynamic contact angle of the resin surface with respect to the temperature change measured in Example 5.

FIG. 7 is a graph showing the results of the dynamic contact angle of the resin surface with respect to the temperature change measured in Example 6.

FIG. 8 is a graph showing the results of the dynamic contact angle of the resin surface with respect to the temperature change measured in Example 7.

Claims (1)

[Claims] 1. When evaluating the surface characteristics of a resin by dynamic contact angle measurement, the dynamic contact angle measurement is measured by changing the temperature of the liquid with respect to a liquid containing water and / or an organic solvent. A method for evaluating resin surface characteristics, comprising: