JP2005181179A - Method of measuring oxygen consumption rate in membrane material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an in-membrane oxygen consumption rate measuring method for a membrane material, capable of measuring easily and quickly an oxygen consumption rate consumed, by imparting energy in the inorganic or organic membrane material. <P>SOLUTION: In this in-membrane oxygen consumption rate measuring method for the membrane material for measuring the oxygen consumption rate consumed in the membrane material, by imparting a means for changing an in-membrane oxygen permeation rate in the membrane material; the membrane material is bonded onto a tip of an oxygen electrode; the oxygen permeation rate is found, based on a numeral value varied, in response to oxygen amounts in the membrane material, measured by the oxygen electrode, before and after imparting the means, and the difference between the oxygen permeation rates before and after imparting the means is determined as the oxygen consumption rate. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for measuring an oxygen consumption rate in a film material such as an inorganic film material or an organic film material.

For example, photo-oxygen consumption behavior due to light sensitive materials, inorganic film materials such as polymer films, additives in organic film materials, and color materials is important in polymer degradation, image light resistance, stain analysis, etc. Conventionally, analysis of the oxygen balance in the film material has not been possible because the oxygen consumption rate is unknown. The measurement of oxygen consumption rate in soil and water by microorganisms, plants, etc. is generally performed, and the oxygen consumption rate automatic measuring device that automatically measures the consumption rate of oxygen consumed by seeds such as barley is It is known (for example, refer to Patent Document 1). However, a method for quickly and simply estimating the oxygen consumption behavior in the film material has not been known. In particular, there has been no known example of analyzing the oxygen consumption rate in the case of applying energy in a film material.
Japanese Patent Laid-Open No. 2003-4721

  An object of the present invention is to provide an oxygen consumption rate of a membrane material that can easily and quickly measure the consumption rate of oxygen consumed by providing a means for changing the oxygen transmission rate in the membrane of an inorganic film material or an organic film material. It is to provide a measurement method.

Means for solving the above-mentioned problems are as follows.
<1> A method for measuring an in-film oxygen consumption rate of a film material by measuring a consumption rate of oxygen consumed in the film material by providing a means for changing the oxygen transmission rate in the film material to the film material. The membrane material is affixed to the tip of an oxygen electrode, and the oxygen permeation rate is obtained from a numerical value measured by the oxygen electrode, which varies depending on the amount of oxygen in the membrane material before and after application of the means. Furthermore, the oxygen consumption rate measurement method of the membrane material is characterized in that a difference in oxygen transmission rate before and after the provision of the means is defined as an oxygen consumption rate in the membrane.

<2> The method for measuring an oxygen consumption rate of a film material according to <1>, wherein a polarographic oxygen electrode is used as the oxygen electrode.

<3> The method for measuring an oxygen consumption rate of a membrane material according to <1> or <2>, wherein the means for changing the oxygen transmission rate in the membrane is energy, an external stimulus, or an additive It is.

<4> The method for measuring an oxygen consumption rate of a film material according to <3>, wherein the means for changing the oxygen transmission rate in the film is energy.

<5> The method for measuring an oxygen consumption rate of a film material according to <4>, wherein light is used as the energy.

  According to the present invention, the oxygen consumption rate of the membrane material that can easily and quickly measure the consumption rate of oxygen consumed by providing means for changing the oxygen transmission rate in the membrane in the inorganic membrane material or the organic membrane material. Can be provided.

Hereinafter, the present invention will be described in detail.
The method for measuring the oxygen consumption rate of a membrane material according to the present invention provides a membrane material for measuring the consumption rate of oxygen consumed in the membrane material by providing the membrane material with means for changing the oxygen transmission rate in the membrane. A method for measuring an oxygen consumption rate in a film, wherein the amount of oxygen in the film material before and after application of the means is measured by applying the film material to the tip of an oxygen electrode and measuring with the oxygen electrode The oxygen permeation rate is obtained from a numerical value that varies according to the above, and the difference in oxygen permeation rate before and after applying the means is defined as the oxygen consumption rate in the film.
Here, the “numerical value varying according to the amount of oxygen in the film material” refers to an oxygen concentration value, a voltage indicated by the oxygen electrode, and the like. Numerical values such as oxygen concentration value and voltage are measured by an oxygen electrode.
Hereinafter, a method for measuring the oxygen consumption rate of the film material of the present invention will be described in detail.

  First, an example of the process in the method for measuring the oxygen consumption rate of the film material of the present invention will be described with reference to the drawings. FIG. 1 is a conceptual diagram showing an oxygen electrode 12 to which a membrane material 10 is attached. In FIG. 1, the dimensions of the membrane material 10 and the oxygen electrode 12 are exaggerated and do not correspond to the actual dimension ratio. The oxygen electrode 12 is a polarographic oxygen electrode, and an electrode diaphragm 12a is disposed therein. The oxygen electrode 12 is used in a power supply device that applies a voltage (not shown), a display device (recorder) that monitors an oxygen concentration value, and the like. It is connected. In the state shown in FIG. 1, an oxygen concentration value based on a current (voltage) proportional to the amount of oxygen in the film material 10 is displayed on the display device. In FIG. 1, the thickest arrow line indicates the permeation of oxygen to the membrane material 10.

  Before measuring the oxygen consumption rate of the membrane material, in order to convert the oxygen concentration value in the membrane material into the oxygen transmission rate of the membrane material, a membrane sample having a known oxygen transmission rate with respect to the oxygen concentration value is prepared. Based on the oxygen transmission rate with respect to the oxygen concentration value of the membrane sample, the oxygen transmission rate of the membrane material to be measured can be uniquely determined from the oxygen concentration value indicated by the oxygen electrode described later. The relationship between the oxygen concentration value and the oxygen transmission rate of the membrane sample may be previously set as a function or a calibration curve. In any case, the oxygen transmission rate is calculated from the oxygen concentration value. Is preferably obtained instantaneously.

Next, with reference to the diagram shown in FIG. 2, the measurement process of the oxygen consumption rate in the present invention will be described with an example using energy application, which is a preferred embodiment. The following (1) to (9) correspond to the steps (1) to (9) in FIG.
(1) Affixing the membrane material to the tip of the oxygen electrode As shown in FIG. 1, the membrane material 10 whose oxygen consumption rate is to be measured is affixed to the tip of the oxygen electrode 12 via silicon grease or the like.
(2) Wait until the oxygen concentration reaches a steady state With the membrane material 10 applied to the oxygen electrode 12, the oxygen concentration value is displayed by a display device (not shown) that displays the oxygen concentration value connected to the oxygen electrode 12. Monitor and wait until a steady state is reached where the oxygen concentration in the membrane material 10 is constant (does not change over time).
(3) Confirmation that oxygen concentration is in steady state It is confirmed that the oxygen concentration value is in a steady state, and the oxygen concentration value at that time is measured by the display device.

(4) Conversion from the oxygen concentration value in the steady state to the oxygen transmission rate (A) The oxygen concentration value of the membrane material 10 in the steady state is converted into the oxygen transmission rate based on the above-described membrane sample. Specifically, the oxygen transmission rate of the membrane material with respect to the oxygen concentration value of the membrane sample in which the measured oxygen concentration value and the oxygen concentration value of the membrane sample are the same is defined as the oxygen transmission rate of the membrane material 10. The value thus converted is defined as oxygen transmission rate (A) (oxygen transmission rate before energy application).
(5) Start of energy application In a steady state, light (energy) (indicated by three arrows in FIG. 1) is irradiated (applied) from the side opposite to the side of the membrane material 10 attached to the oxygen electrode. . Then, oxygen is consumed by the substance that consumes oxygen contained in the film material 10 by the applied energy (light), and oxygen reaching the oxygen electrode 12 decreases, that is, the oxygen transmission rate of the film material 10 decreases.
(6) Wait until the oxygen concentration reaches a steady state Further, while continuing to give energy, the oxygen concentration value is continuously monitored, and waits until the oxygen concentration value of the film material 10 reaches the steady state.

(7) Confirm that the oxygen concentration is in a steady state Confirm that the oxygen concentration value is in a steady state, and measure the oxygen concentration value at that time using the display device.
(8) Conversion from the oxygen concentration value in the steady state to the oxygen transmission rate (B) The oxygen concentration value measured in the steady state is the oxygen after energy application based on the above-mentioned film sample in the same manner as in the step (4). Convert to transmission speed. And the value converted in this way is defined as oxygen transmission rate (B) (oxygen transmission rate after energy application).
(9) The calculated value of the difference in oxygen permeation rate before and after energy application (AB) is the oxygen consumption rate in the film. The oxygen permeation rate of the membrane material before energy application calculated in step (4) (A) Then, the oxygen transmission rate (B) of the membrane material after energy application calculated in the step (8) is subtracted, and the calculated value is used as the oxygen consumption rate in the membrane.

  The above is a method for measuring the oxygen concentration value displayed on the display device connected to the oxygen electrode, and converting the oxygen concentration value into the oxygen transmission rate to obtain the oxygen consumption rate. Since the amount of oxygen in the membrane material can be uniquely known from the voltage, the oxygen transmission rate may be obtained from the output voltage, and the oxygen consumption rate may be obtained from the oxygen transmission rate.

  As described above, the oxygen transmission rate before energy application is the oxygen transmission rate when the oxygen transmission rate of the film material reaches a steady state after the membrane material is attached to the oxygen electrode. The oxygen transmission rate is the oxygen transmission rate when a steady state is reached by continuously applying energy. Here, the steady state does not mean that the oxygen permeation rate is necessarily constant, but also includes a state where the oxygen permeation rate decreases at a constant rate of change.

  The oxygen permeation rate and oxygen consumption rate in the state where the membrane material is attached to the oxygen electrode will be considered. As shown in FIG. 3, the oxygen permeation rate of the membrane material decreases with the passage of time, and reaches a steady state after a certain period of time. Now, when the film material is irradiated with light (on in FIG. 3), oxygen is consumed in the film material and the oxygen transmission rate decreases. The difference between the oxygen transmission rate in the steady state of FIG. 3 and the oxygen transmission rate at the time of energy application is the oxygen consumption rate (oxygen consumption per unit time).

FIG. 4 shows the oxygen transmission rate (cm ³ / m ² · day) when a cyan layer (layer thickness: 8.0 μm) of a thermosensitive recording material is used as a film material and the cyan layer is irradiated with light having an illuminance of 5000 lux. The change with time is shown. In the steady state, the oxygen transmission rate decreases at a constant slope (rate of change). However, when light irradiation is started (ON in FIG. 4), the oxygen transmission rate rapidly decreases and becomes a steady state after a certain period of time. When the irradiation is stopped (OFF in FIG. 4), it rises again and becomes a steady state. The difference between the oxygen transmission rate before light irradiation and the oxygen transmission rate after light irradiation (d in FIG. 4) is the oxygen consumption rate.

  Hereinafter, each component in the measuring method of the oxygen consumption rate of this invention is explained in full detail.

[Membrane material]
In the present invention, examples of the film material capable of measuring the oxygen consumption rate include a heat-sensitive recording layer of a heat-sensitive recording material, a photographic light-sensitive material, a resist material, and a packaging material, and may be a single layer or a multilayer. The present invention is particularly effective for a film material containing a substance that consumes oxygen.
As thickness of film | membrane material, it can be set within the range of 1-20 micrometers, for example.

[Oxygen electrode]
The oxygen electrode can be broadly classified into a polarographic system and an air battery system. The former is a type in which a voltage is applied from the outside to cause an oxidation-reduction reaction, and a current (voltage) proportional to the oxygen concentration flowing at that time is measured. The latter is a type that measures the current flowing in accordance with the amount of oxygen without applying a voltage from the outside. In the present invention, a polarographic oxygen electrode is particularly preferable.
Moreover, it is preferable to use an electrode diaphragm disposed inside the oxygen electrode that has a high response speed and high sensitivity.

[Means for changing oxygen transmission rate]
In the present invention, examples of means for changing the oxygen transmission rate include application of energy such as light, application of external stimuli such as pH and humidity, and inclusion of additives such as oxygen absorbers and aerobic bacteria. Preferably it is energy.
In the present invention, examples of the energy applied to the film material attached to the oxygen electrode include electromagnetic waves, that is, radiation rays such as heat rays, visible rays, ultraviolet rays, and X-rays, and heat. Specific examples of devices that output such energy include fluorescent lamps, ultraviolet irradiation lamps, ultrasonic generators, laser light sources, and X-ray sources. In particular, in the present invention, light is effective as energy.
In the present invention, since the oxygen consumption rate under the energy application of an arbitrary film material is measured, the energy to be applied is not particularly limited, and the energy is arbitrarily selected for the film material to be measured. What is necessary is just to provide to film | membrane material. However, the energy which promotes consumption of oxygen by giving is preferable.
In addition, when heat is applied as energy, the oxygen transmission rate of the film material may change due to heat. In this case, it is necessary to examine in advance the oxygen permeation rate change due to the heat of the film to which no oxygen consuming substance is added.

  The above method for measuring the oxygen consumption rate of the membrane material of the present invention can be applied to the measurement of the consumption rate of a deterioration inhibitor that prevents deterioration due to oxygen, for example, used for a film such as a packaging material. Or it can apply also to the decomposition rate measurement of the coloring material etc. in a coating film.

  As described above, in the present invention, the measurement of the oxygen consumption rate in the film material uses a general-purpose oxygen electrode without using a complicated measuring apparatus, so that the oxygen consumption rate can be adjusted easily and quickly. Measurements can be performed.

  Hereinafter, although the measuring method of the oxygen consumption rate of the film | membrane material of this invention is concretely demonstrated by an Example, this invention is not limited to a following example. In the examples below, “part” means “part by mass” unless otherwise specified, and “%” means “% by mass” unless otherwise specified.

[Example 1]
<Production of membrane material>
First, as a film material used for measuring the oxygen consumption rate, a heat-sensitive recording material A that develops cyan was produced. A method for producing the thermosensitive recording material A will be described below.

-Preparation of coating solution for thermosensitive recording layer-
(Preparation of phthalated gelatin solution)
Phthalated gelatin (trade name: MGP gelatin, manufactured by Nippi Collagen Co., Ltd.) 32 parts, 1,2-benzothiazolin-3-one (3.5% methanol solution, manufactured by Daito Chemical Industry Co., Ltd.) 0.9143 Part and 367.1 parts of ion-exchanged water were mixed and dissolved at 40 ° C. to obtain a phthalated gelatin aqueous solution.
(Preparation of alkali-treated gelatin solution)
25.5 parts of alkali-treated low ion gelatin (trade name; # 750 gelatin, manufactured by Nitta Gelatin Co., Ltd.), 1,2-benzothiazolin-3-one (3.5% methanol solution, Daito Chemical Industry Co., Ltd.) )) 0.7286 parts, calcium hydroxide 0.153 parts, and ion-exchanged water 143.6 parts were mixed and dissolved at 50 ° C. to obtain an alkali-treated gelatin solution.

(Preparation of electron-donating dye precursor-encapsulated microcapsule solution (c))
A mixture of 7.6 parts of the following electron donating dye (H), 1-methylpropylphenyl-phenylmethane and 1- (1-methylpropylphenyl) -2-phenylethane (trade name; Hysol SAS-310 (manufactured by Shin Nippon Petrochemical Co., Ltd.) 8.0 parts, 8.0 parts of the following compound (I) (trade name; Irgaperm 2140 Ciba Geigy Co., Ltd.) was added, heated and dissolved uniformly. did. 7.2 parts of xylylene diisocyanate / trimethylolpropane adduct (trade name; Takenate D110N (75% ethyl acetate solution), manufactured by Mitsui Takeda Chemical Co., Ltd.) as a capsule wall material and polymethylene polyphenyl polyisocyanate (Product name: Millionate MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 5.3 parts thereof were added and stirred uniformly to obtain a liquid mixture (IX).

Separately, 28.8 parts of the above aqueous phthalated gelatin solution, 9.5 parts of ion-exchanged water, 0.17 part of Scraph AG-8 (50%; manufactured by Nippon Seika Co., Ltd.) and sodium dodecylbenzenesulfonate (10% aqueous solution) ) 4.3 parts were added and mixed to obtain a mixed solution (X).
The mixed solution (IX) was added to the mixed solution (X), and the mixture was emulsified and dispersed at 40 ° C. using a homogenizer (manufactured by Nippon Seiki Seisakusho). To the obtained emulsion, 50 parts of water and 0.12 part of tetraethylenepentamine are homogenized, and the mixture is stirred at 65 ° C. for 3 hours while removing ethyl acetate, so that the solid content concentration of the capsule liquid is 33. The microcapsule solution was obtained by adjusting the concentration so that the concentration became%. The obtained microcapsules had a median diameter of 1.00 μm as a result of particle size measurement (LA-700, measured by Horiba, Ltd.).
Furthermore, with respect to 100 parts of the microcapsule solution, 3.7 parts of sodium dodecylbenzenesulfonate 25% aqueous solution (trade name: Neoperex F-25, manufactured by Kao Corporation) and 4,4′-bistriazinylaminostilbene A fluorescent whitening agent (trade name: Kaycoll BXNL, manufactured by Nippon Soda Co., Ltd.) containing -2,2'-disulfone derivative was added and stirred uniformly to obtain a microcapsule dispersion (c). It was.

(Preparation of electron-accepting compound dispersion (c))
11.3 parts of the phthalated gelatin aqueous solution, 30.1 parts of ion-exchanged water, 15 parts of 4,4 ′-(p-phenylenediisopropylidene) diphenol (trade name; bisphenol P, manufactured by Mitsui Petrochemical Co., Ltd.) 3.8 parts of 2% -2-ethylhexyl sodium succinate aqueous solution was added and dispersed overnight with a ball mill to obtain a dispersion. The solid content concentration of this dispersion was 26.6%.
After adding 45.2 parts of the alkali-treated gelatin aqueous solution to 100 parts of the dispersion and stirring for 30 minutes, ion-exchanged water was added so that the solids concentration of the dispersion was 23.5%. A compound dispersion (c) was obtained.

(Preparation of coating solution for thermosensitive recording layer)
The electron-donating dye precursor-encapsulated microcapsule liquid (c) and the electron-accepting compound dispersion liquid (c) are mixed so that the mass ratio of the electron-accepting compound / electron-donating dye precursor is 10/1. Thus, a thermal recording layer coating solution was obtained.

<Production of membrane material>
The cyan layer coating solution was applied to a polyethylene base and dried, and peeled to obtain a film material. A film material having a thickness in the range of 5 to 20 μm was used. The measurement temperature and humidity were 25 ° C. and 50% RH.

<Measurement preparation>
As an oxygen electrode, model 3600 manufactured by Orbis Fair Laboratories Japan Inc. was used. As the electrode diaphragm, polyfluoroalkoxy (PFA) 2956A having the fastest response speed and high sensitivity was used. Silicone grease (SH111, manufactured by Toray Dow Corning Silicone Co., Ltd.) was thinly applied to the electrode diaphragm, and the film material was adhered thereon. It has been confirmed that the coating film of silicon grease does not affect the oxygen transmission rate and the consumption rate.

<Data processing method>
An oxygen concentration value indicated by the electrode was converted into an oxygen transmission rate (cm ³ / m ² · day) using a membrane sample (polyethylene terephthalate) having a known oxygen transmission rate relative to the oxygen concentration value.

<Measurement>
Measurement of the oxygen consumption rate was carried out according to the diagram shown in FIG.
A membrane material was affixed to the tip of the oxygen electrode (step (1)) and waited until the measured oxygen concentration reached a steady state (step (2)). It was confirmed that the oxygen concentration reached a steady state (step (3)), and the oxygen concentration value in the steady state was converted to an oxygen transmission rate based on the data processing method (step (4)). This oxygen transmission rate was defined as the oxygen transmission rate (A) before energy application (fluorescent lamp irradiation). Thereafter, light irradiation (energy application) was started on the membrane sample attached to the oxygen electrode with a fluorescent lamp (step (5)). The illuminance range was 0 to 15000 lux. In order to prevent errors due to temperature rise due to irradiation, the oxygen electrode was air-cooled and the oxygen electrode temperature was also monitored. After light irradiation, it waited until the oxygen concentration reached a steady state (step (6)). It was confirmed that the oxygen concentration reached a steady state (step (7)), and the oxygen concentration value in the steady state was converted to an oxygen transmission rate based on the data processing method (step (8)). This oxygen transmission rate was defined as the oxygen transmission rate (B) after energy application (fluorescence lamp irradiation). Subsequently, the fluorescent lamp irradiation was stopped, and it was confirmed that the oxygen concentration value was restored. Finally, the oxygen transmission rate (B) was subtracted from the oxygen transmission rate (A) to determine the oxygen consumption rate in the film (step (9)). In FIG. 5, the oxygen consumption rate with respect to the illumination light quantity of the irradiated light is shown with a graph.

The main steps of the above method for measuring the oxygen consumption rate are shown by specific numerical values. First, the oxygen electrode before application of the film to be measured exhibited an oxygen concentration value in air of around 21%. By attaching the membrane material, the oxygen concentration value decreased to 6180 ppm and became a steady state. According to the calibration curve, this value corresponds to a transmission amount of 76.0 cm ³ / m ² · day. When 5,000 lux fluorescent light was irradiated in this state, the oxygen concentration value decreased by 41 ppm and reached a steady state at 6139 ppm. Similarly, this value corresponds to 75.5 cm ³ / m ² · day according to the calibration curve. Therefore, a difference of 0.5 cm ³ / m ² · day with or without light irradiation is the oxygen consumption rate.

[Example 2]
A film material was produced in the same manner as the film material produced in Example 1, and the film material was changed to a time of 1 to 10 seconds with a heat stamp at 160 ° C. The film | membrane material which has was produced. Then, the color density (OD) of the printed portion was measured with a Macbeth densitometer. FIG. 6 is a graph showing the relationship between the color density of this film material and the oxygen consumption rate at a thickness of 80 μm and a fluorescent lamp 5000 lux. FIG. 6 shows that the oxygen consumption rate decreases as the color density of the color development portion of the film material after printing increases.

[Example 3]
<Production of membrane material>
In this embodiment, the heat-sensitive recording material B in which a magenta layer, an intermediate layer, a yellow layer, an intermediate layer, a light transmittance adjusting layer, and a protective layer are laminated on a base is used as a film material. First, preparation of the coating solution for each layer is shown below.

(1) Preparation of coating solution for yellow layer <Preparation of microcapsule liquid (a) encapsulating diazonium salt compound>
To 16.1 parts of ethyl acetate, 2.2 parts of the following diazonium compound (A) (maximum absorption wavelength 420 nm), 2.2 parts of the following diazonium compound (B) (maximum absorption wavelength 420 nm), 7.2 parts of monoisopropylbiphenyl, Add 2.4 parts of diphenyl phthalate and 0.4 part of diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide (trade name: Lucillin TPO, manufactured by BASF Japan Ltd.) and heat to 40 ° C. And evenly dissolved. A mixture of xylylene diisocyanate / trimethylolpropane adduct and xylylene diisocyanate / bisphenol A adduct as a capsule wall material (trade name; Takenate D119N (50% ethyl acetate solution), manufactured by Takeda Pharmaceutical Co., Ltd.) 8.6 parts was added and stirred uniformly to obtain a mixture (I).

Separately, 16.3 parts of ion-exchanged water and 0.34 part of Scraph AG-8 (50%; manufactured by Nippon Seika Co., Ltd.) were added to 58.6 parts of the phthalated gelatin aqueous solution shown in Example 1, and the mixture was mixed. (II) was obtained.
The mixed solution (I) was added to the mixed solution (II), and the mixture was emulsified and dispersed at 40 ° C. using a homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd.). After adding 20 parts of water to the obtained emulsion and homogenizing it, the mixture was stirred at 40 ° C. to carry out an encapsulation reaction for 3 hours while removing ethyl acetate. Thereafter, 4.1 parts of ion exchange resin Amberlite IRA68 (manufactured by Organo Corp.) and 8.2 parts of Amberlite IRC50 (manufactured by Organo Corp.) were added and further stirred for 1 hour. Thereafter, the ion exchange resin was removed by filtration, and the concentration was adjusted so that the solid content concentration of the capsule liquid was 20.0% to obtain a diazonium salt compound-encapsulating microcapsule liquid (a). The obtained microcapsules had a median diameter of 0.36 μm as a result of particle size measurement (LA-700, manufactured by Horiba, Ltd.).

<Preparation of coupler compound emulsion (a)>
33.0 parts of ethyl acetate, 9.9 parts of the following coupler compound (C), 13.9 parts of triphenylguanidine (manufactured by Hodogaya Chemical Co., Ltd.), 4,4 ′-(m-phenylenediisopropylidene) diphenol (Brand name; Bisphenol M (Mitsui Petrochemical Co., Ltd.)) 16.8 parts, 3,3,3 ′, 3′-tetramethyl-5,5 ′, 6,6′-tetra (1-propyloxy) -1,1'-spirobisindane 3.3 parts, 4- (2-ethylhexyloxy) benzenesulfonic acid amide (manac) 13.6 parts, 4-n-pentyloxybenzenesulfonic acid amide (Manac And 6.8 parts calcium dodecylbenzenesulfonate (trade name: Pionein A-41-C, 70% methanol solution, Takemoto Yushi Co., Ltd.) 4.2 parts. III)

Separately, 107.3 parts of ion-exchanged water was mixed with 206.3 parts of the alkali-treated gelatin aqueous solution shown in Example 1 to obtain a mixed liquid (IV).
The mixed solution (III) was added to the mixed solution (IV), and the mixture was emulsified and dispersed at 40 ° C. using a homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd.). The obtained coupler compound emulsion was heated under reduced pressure to remove ethyl acetate, and then the concentration was adjusted so that the solid content concentration was 26.5%. The particle size of the obtained coupler compound emulsion was 0.21 μm in median diameter as a result of particle size measurement (LA-700, measured by HORIBA, Ltd.).
Further, 9 parts of SBR latex (trade name: SN-307, 48% solution, manufactured by Sumika Aves Latex Co., Ltd.) adjusted to 26.5% are added to 100 parts of the above coupler compound emulsion. The mixture was stirred uniformly to obtain a coupler compound emulsion (a).

<Preparation of yellow layer coating solution (a)>
The diazonium salt compound-encapsulating microcapsule liquid (a) and the coupler compound-emulsified liquid (a) are mixed so that the mass ratio of the encapsulating coupler compound / diazo compound is 2.2 / 1, and the yellow layer A coating solution (a) was obtained.

(2) Preparation of coating solution for magenta layer <Preparation of diazonium salt compound-encapsulated microcapsule solution (b)>
15.1 parts of ethyl acetate, 2.8 parts of the following diazonium compound (D) (maximum absorption wavelength 365 nm), 3.0 parts of diphenyl phthalate, 4.7 parts of phenyl 2-benzoyloxybenzoate and the following ester compound (product) Name: 4.2 parts of light ester TMP, manufactured by Kyoei Yushi Chemical Co., Ltd.) and 0.1 parts of calcium dodecylbenzenesulfonate (trade name: Pionein A-41-C, 70% methanol solution, Takemoto Yushi Co., Ltd.) Was added and heated to dissolve uniformly. A mixture of xylylene diisocyanate / trimethylolpropane adduct and xylylene diisocyanate / bisphenol A adduct as a capsule wall material (trade name; Takenate D119N (50% ethyl acetate solution), manufactured by Takeda Pharmaceutical Co., Ltd.) ) 2.5 parts and 6.8 parts of xylylene diisocyanate / trimethylolpropane adduct (trade name; Takenate D110N (75% ethyl acetate solution), Takeda Pharmaceutical Co., Ltd.) are added and stirred uniformly. A liquid (V) was obtained.

Separately, 21.0 parts of ion-exchanged water was added to and mixed with 55.3 parts of the phthalated gelatin aqueous solution shown in Example 1 to obtain a mixed liquid (VI).
The mixed solution (V) was added to the mixed solution (VI), and the mixture was emulsified and dispersed at 40 ° C. using a homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd.). After adding 24 parts of water to the obtained emulsion and homogenizing it, the mixture was stirred at 40 ° C. for 3 hours while removing ethyl acetate. Thereafter, 4.1 parts of ion exchange resin Amberlite IRA68 (manufactured by Organo Corp.) and 8.2 parts of Amberlite IRC50 (manufactured by Organo Corp.) were added and further stirred for 1 hour. Thereafter, the ion exchange resin was removed by filtration, and the concentration was adjusted so that the solid content of the capsule liquid was 20.0%, whereby a diazonium salt compound-encapsulating microcapsule liquid (b) was obtained. The obtained microcapsules had a median diameter of 0.43 μm as a result of particle size measurement (LA-700, manufactured by Horiba, Ltd.).

<Preparation of coupler compound emulsion (b)>
16.9 parts of the following coupler compound (E) and 10.0 parts of triphenylguanidine (manufactured by Hodogaya Chemical Co., Ltd.), 4,4 ′-(m-phenylenediisopropylidene) diphenol (36.9 parts of ethyl acetate) Product Name: Bisphenol M (Mitsui Petrochemical Co., Ltd.) 18.0 parts, 1,1- (p-hydroxyphenyl) -2-ethylhexane 14 parts, 3,3,3 ′, 3′-tetramethyl -5,5 ', 6,6'-tetra (1-propyloxy) -1,1'-spirobisindane 3.5 parts, 3.5 parts of the following compound (G), tricresyl phosphate 1.7 parts, malein 0.8 parts of diethyl acid and 4.5 parts of calcium dodecylbenzenesulfonate (trade name: Piionin A-41-C, 70% methanol solution, Takemoto Yushi Co., Ltd.) were dissolved to obtain a mixture (VII). .

Separately, 107.3 parts of ion-exchanged water was mixed with 206.3 parts of the alkali-treated gelatin aqueous solution shown in Example 1 to obtain a mixed liquid (VIII).
The mixed solution (VII) was added to the mixed solution (VIII), and the mixture was emulsified and dispersed at 40 ° C. using a homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd.). The resulting coupler compound emulsion was heated under reduced pressure to remove ethyl acetate, and then the concentration was adjusted so that the solid content concentration was 24.5% to obtain a coupler compound emulsion (b). The obtained coupler compound emulsion had a median diameter of 0.22 μm as a result of particle size measurement (LA-700, measured by Horiba, Ltd.).

<Preparation of coating liquid (b)>
The diazonium salt compound-encapsulated microcapsule liquid (b) and the coupler compound-emulsified liquid (b) were mixed so that the mass ratio of the encapsulated coupler compound / diazo compound was 3.5 / 1. Further, an aqueous solution (5%) of polystyrene sulfonic acid (partially potassium hydroxide neutralized) was mixed so as to be 0.2 parts with respect to 10 parts of the capsule liquid amount to obtain a magenta layer coating liquid (b). .

(3) Preparation of coating solution for intermediate layer Alkali-treated low ion gelatin (trade name; # 750 gelatin, manufactured by Nitta Gelatin Co., Ltd.) 100.0 parts, 1,2-benzothiazoline-3-one (3.5 % Methanol solution, manufactured by Daito Chemical Industry Co., Ltd.) 2.857 parts, calcium hydroxide 0.5 parts, and ion-exchanged water 521.643 parts were mixed and dissolved at 50 ° C. to prepare an intermediate layer gelatin aqueous solution. Got.

  10.0 parts gelatin aqueous solution for preparing the intermediate layer, 0.05 parts sodium (4-nonylphenoxytrioxyethylene) butyl sulfonate (manufactured by Sankyo Chemical Co., Ltd., 2.0% aqueous solution), boric acid (4. 2.07 parts of 0% aqueous solution), 0.19 parts of polystyrenesulfonic acid (partially potassium hydroxide neutralized) aqueous solution (5%), 4% aqueous solution of the following compound (J) (manufactured by Wako Pure Chemical Industries, Ltd.) 3.42 parts, 1.13 parts of a 4% aqueous solution of the following compound (J ′) (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.67 parts of ion-exchanged water were mixed to obtain an intermediate layer coating solution.

(4) Preparation of coating solution for adjusting light transmittance <Preparation of UV absorber precursor microcapsule solution>
14.5 parts of [2-allyl-6- (2H-benzotriazol-2-yl) -4-t-octylphenyl] benzenesulfonate as an ultraviolet absorber precursor in 71 parts of ethyl acetate, 2,2′-t -4.0 parts of octyl hydroquinone, 2.9 parts of tricresyl phosphate, 5.7 parts of α-methylstyrene dimer (trade name: MSD-100, manufactured by Mitsui Chemicals, Inc.), calcium dodecylbenzenesulfonate (trade name: Pionein A) 0.45 part of -41-C (70% methanol solution), Takemoto Yushi Co., Ltd.) was dissolved and dissolved uniformly. Add 54.7 parts of xylylene diisocyanate / trimethylolpropane adduct (trade name; Takenate D110N (75% ethyl acetate solution), Takeda Pharmaceutical Co., Ltd.) as a capsule wall material to the above mixture and stir uniformly. An ultraviolet absorber precursor mixture was obtained.

  Separately, 8.9 parts of 30% phosphoric acid aqueous solution and 532.6 parts of ion-exchanged water were mixed with 52 parts of itaconic acid-modified polyvinyl alcohol (trade name: KL-318, manufactured by Kuraray Co., Ltd.), and ultraviolet absorber precursor micro A PVA aqueous solution for capsule liquid was prepared.

  The UV absorber precursor mixed solution was added to 516.06 parts of the PVA aqueous solution for the UV absorber precursor microcapsule solution, and the mixture was emulsified and dispersed at 20 ° C. using a homogenizer (manufactured by Nippon Seiki Seisakusho Co., Ltd.). . After adding 254.1 parts of ion-exchanged water to the obtained emulsion and homogenizing it, an encapsulation reaction was carried out for 3 hours with stirring at 40 ° C. Thereafter, 94.3 parts of ion exchange resin Amberlite MB-3 (manufactured by Organo Corporation) was added, and the mixture was further stirred for 1 hour. Thereafter, the ion exchange resin was removed by filtration, and the concentration was adjusted so that the solid concentration of the capsule liquid was 13.5%. The obtained microcapsules had a median diameter of 0.23 ± 0.05 μm as a result of particle size measurement (LA-700, manufactured by Horiba, Ltd.). To this capsule solution 859.1 parts, carboxy-modified styrene butadiene latex (trade name: SN-307, (48% aqueous solution), manufactured by Sumitomo Nougatac Co., Ltd.) 2.416 parts and ion-exchanged water 39.5 parts were mixed. An ultraviolet absorber precursor microcapsule solution was obtained.

<Preparation of coating solution for light transmittance adjusting layer>
1000 parts of the above-mentioned ultraviolet absorber precursor microcapsule liquid, the following compound (K) (trade name: Megafax F-120, 5% aqueous solution, Dainippon Ink & Chemicals, Inc.) 5.2 parts, 4% sodium hydroxide 7.75 parts of aqueous solution and 73.39 parts of sodium (4-nonylphenoxytrioxyethylene) butyl sulfonate (manufactured by Sankyo Chemical Co., Ltd., 2.0% aqueous solution) are mixed, and the coating solution for light transmittance adjusting layer Got.

(5) Preparation of protective layer coating solution <Preparation of protective layer polyvinyl alcohol solution>
160 parts of 4% vinyl alcohol-alkyl vinyl ether copolymer (trade name: EP-130, manufactured by Denki Kagaku Kogyo Co., Ltd.), mixed solution of sodium alkyl sulfonate and polyoxyethylene alkyl ether phosphate (trade name: Neoscore) CM-57, (54% aqueous solution), manufactured by Toho Chemical Industry Co., Ltd.) 8.74 parts and 3832 parts of ion-exchanged water were mixed and dissolved at 90 ° C. for 1 hour to obtain a uniform polyvinyl alcohol solution for a protective layer. Got.

<Preparation of pigment dispersion for protective layer>
Barium sulfate (trade name: BF-21F, barium sulfate content 93% or more, manufactured by Sakai Chemical Industry Co., Ltd.) 8 parts anionic special polycarboxylic acid type polymer activator (trade name: Poise 532A (40% Aqueous solution), produced by Kao Co., Ltd.) 0.2 part and ion-exchanged water 11.8 parts were mixed and dispersed by dynomill to prepare a barium sulfate dispersion. As a result of particle size measurement (LA-910, manufactured by HORIBA, Ltd.), this dispersion was found to have a median diameter of 0.15 μm or less.
10.1 parts of colloidal silica (trade name: Snowtex O (20% aqueous dispersion), manufactured by Nissan Chemical Co., Ltd., average particle size 20 nm) is added to 45.6 parts of the barium sulfate dispersion. A pigment dispersion for protective layer was obtained.

<Preparation of protective layer matting agent dispersion>
190 parts of wheat starch (trade name: Wheat Starch S, manufactured by Shinshin Food Industry Co., Ltd.) and an aqueous dispersion of 1-2 benzisothiazoline 3-one (trade names: PROXEL BD, manufactured by IC Corporation) ) 3.81 parts and 1976.19 parts of ion exchange water were mixed and dispersed uniformly to obtain a protective layer matting agent dispersion.

<Preparation of coating solution for protective layer>
1000 parts of the polyvinyl alcohol solution for the protective layer is mixed with the above compound (K) (trade name: Megafax F-120, 5% aqueous solution, Dainippon Ink & Chemicals, Inc.), 40 parts (4-nonylphenoxytrioxyethylene) 50 parts of sodium butyl sulfonate (manufactured by Sankyo Chemical Co., Ltd., 2.0% aqueous solution), 49.87 parts of the pigment dispersion for protective layer, 16.65 parts of the matting agent dispersion for protective layer, zinc stearate Dispersion (trade name: Hymicron LIII, 21.5% aqueous solution, manufactured by Chukyo Yushi Co., Ltd.) 48.7 parts, acrylic silicone modified emulsion (trade name: ARJ-2A, 44 mass% dispersion, Nippon Pure Chemical ( Co., Ltd.) 4.65 parts and ion-exchanged water 275.35 parts were uniformly mixed to obtain a protective layer coating solution.

(6) Production of film material From the bottom to the surface of the PET 100 μm unprimed base, the magenta layer coating solution (b), the intermediate layer (intermediate layer B) coating solution, the yellow layer coating solution (a), Five layers of the light transmittance adjusting layer coating solution and the protective layer coating solution were successively applied in this order, and dried under conditions of 30 ° C./humidity 30% and 40 ° C./humidity 30%. After drying, the coating film was peeled from the base to obtain a film material. The thickness of the film material was 20 μm.
At this time, the coating amount of the yellow layer coating liquid (a) was adjusted so that the coating amount of the diazonium compound (A) contained in the liquid was 0.078 g / m ^{2 in} terms of solid coating amount. The coating amount of the magenta layer coating solution (b) was adjusted such that the coating amount of the diazonium compound (D) contained in the solution was 0.206 g / m ^{2 in} terms of solid coating amount.

The coating solution for the intermediate layer B has a solid content coating amount of 2.38 g / m ² , the light transmittance adjusting layer coating solution has a solid content coating amount of 2.35 g / m ² , and the protective layer coating solution has Application was performed so that the solid content application amount was 1.70 g / m ² .

Next, in the same manner as in Example 1, the obtained film material was irradiated with light with a fluorescent lamp, and the oxygen consumption rate was measured. FIG. 7 shows the relationship between the amount of fluorescent lamp irradiation, the oxygen transmission rate (black circle plot), and the oxygen consumption rate (black square plot). FIG. 7 shows that oxygen is hardly transmitted to the electrode by light irradiation, that is, oxygen consumption of about 1 cm ³ / m ² · day occurs at 5000 lux.

It is the schematic which shows an oxygen electrode and the film | membrane material affixed on this oxygen electrode. It is a figure which shows the measurement procedure in the measuring method of the oxygen consumption rate of the film | membrane material of this invention with a diagram. It is a figure which shows the transition with time of the oxygen permeation rate of a membrane material in a graph. It is a figure which shows the transition with time of the oxygen permeation rate of a membrane material in a graph. It is a figure which shows the oxygen consumption rate with respect to the irradiation light quantity of the light irradiated to the film | membrane material in Example 1 with a graph. It is a figure which shows the relationship between the coloring density of the film | membrane material in Example 2, the thickness of 8.0 micrometers, and the oxygen consumption rate in the fluorescent lamp 5000lux. It is a figure which shows the relationship between the fluorescent lamp irradiation light quantity in Example 3, an oxygen transmission rate, and the oxygen consumption rate calculated | required from it with a graph.

Explanation of symbols

10 membrane material 12 oxygen electrode 12a electrode diaphragm

Claims (5)

A method for measuring an oxygen consumption rate in a membrane material, which measures a consumption rate of oxygen consumed in the membrane material by providing a means for changing the oxygen transmission rate in the membrane to the membrane material,
The membrane material is affixed to the tip of an oxygen electrode, and the oxygen permeation rate is determined from a numerical value that varies according to the amount of oxygen in the membrane material before and after application of the means, measured by the oxygen electrode, Furthermore, the method for measuring the oxygen consumption rate of a membrane material is characterized in that a difference in oxygen transmission rate before and after the application of the means is an oxygen consumption rate in the membrane.   The method for measuring an oxygen consumption rate of a film material according to claim 1, wherein a polarographic oxygen electrode is used as the oxygen electrode.   The method for measuring the oxygen consumption rate of a membrane material according to claim 1 or 2, wherein the means for changing the oxygen transmission rate in the membrane is energy, an external stimulus, or an additive.   The method for measuring the oxygen consumption rate of a membrane material according to claim 3, wherein the means for changing the oxygen transmission rate in the membrane is energy.   5. The method for measuring an oxygen consumption rate of a film material according to claim 4, wherein light is used as the energy.

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