JP5307754B2 - Defect detection method and apparatus for oxygen barrier body - Google Patents

Description

  The present invention relates to a defect detection method and apparatus for an oxygen barrier body.

The quality of food, medicine, etc. is degraded by oxidation. For this reason, an oxygen barrier material having a low oxygen permeability (for example, 10 ⁻² cc / m ² · day · atm) is used as a packaging material for foods and medicines. A film made of the oxygen barrier material (hereinafter referred to as an oxygen barrier film), a container (hereinafter referred to as an oxygen barrier container), or the like is used as a package for food, medicine, or the like.

  In such an oxygen barrier container or the like, there is an inspection (hereinafter referred to as a defect inspection) for examining whether or not there is a site (hereinafter referred to as a defect) through which oxygen easily permeates. As a defect inspection, an oxygen barrier container filled with a substance that changes color by oxidation is exposed to an atmosphere containing oxygen (for example, air), and the position of the defect in the oxygen barrier container is specified from the position of the changed substance. The method is disclosed in Patent Documents 1 and 2.

Japanese Patent Laid-Open No. 54-111390 JP 2007-10382 A

  Conventionally, attempts have been made to manufacture optical devices and electronic devices that have been manufactured based on inorganic substrates based on organic films. This makes it possible to reduce the substrate cost, make it ultra-thin, flexible, etc., and respond to demand trends such as increased product size and wearability.

However, changing the base material of each device to an organic film raises various technical problems. One of them is the low oxygen barrier property of organic films. In order to improve the oxygen barrier property of the organic film, an oxygen barrier film provided with an oxygen barrier property on the organic film is required. Currently, the oxygen permeability of the SiN _X film used as a protective film having an oxygen barrier property of each device is about 10 ⁻² cc / m ² · day · atm. Considering it, it is considered that an oxygen barrier property of about 10 ⁻⁶ to 10 ⁻³ cc / m ² · day · atm is necessary as the oxygen permeability of the oxygen barrier film. Such extremely low oxygen permeability is not limited to the field of devices in which the base material is replaced with an organic film, but is also required for oxygen barrier films such as organic EL elements used in organic EL displays, solar cells, and electronic paper. The

  However, as the oxygen permeability of the oxygen barrier film decreases, the time required for defect inspection increases. Therefore, when an oxygen barrier film having an extremely low oxygen permeability as described above is subjected to defect inspection using the methods described in Patent Documents 1 and 2, the sensitivity of the detector for detecting the discoloration of the substance is sufficient. Therefore, the time required for defect inspection becomes very long. For example, it takes 24 hours to detect a defect formed by inserting a needle having a diameter of 0.2 mm into a container at a depth of 0.05 mm.

  The present invention solves such problems, and an object of the present invention is to provide a defect detection method and apparatus for an oxygen barrier body that enables a defect inspection of the oxygen barrier body to be performed in a short time.

The present invention relates to a defect detection apparatus for an oxygen barrier body that detects chemiluminescence by oxidation to detect defects in a film-like oxygen barrier body, and has a box-shaped container having an opening and a support surface at the periphery of the opening. , and the a vessel to form a sealed space by bonding an oxygen barrier material on the support surface so as to cover the opening, arranged spread toward the opening in a closed space, illuminant and, oxygen to cause chemiluminescent photon counting unit for detecting the number of photons M from light emission body moves along the barrier body, a determination section for determining whether or not the optical child number M exceeds the threshold value N, determine tough "M > If it is determined that N ", and a position detector for detecting the position of the optical element counting unit when detecting the number of photons M.

It is preferable to have a condensing lens provided between the oxygen barrier and the photon counting unit and arranged so that the focal point is located on the entrance window of the photon counting. Moreover, it is a glove box filled with an inert gas, and preferably includes a glove box that provides a space for forming a sealed space.

It is preferable to have a photon detection array in which photon counting units are arranged.

The light emission element, it is preferable to include tetrakis (di main Chiruamino) ethylene.

The present invention also relates to a defect detection method for an oxygen barrier body that detects chemiluminescence by oxidation to detect defects in a film-like oxygen barrier body, and has a box shape having an opening and a support surface at the peripheral edge of the opening. In this vessel, a chemiluminescent substance that emits chemiluminescence is spread out toward the opening, and an oxygen barrier is attached to the support surface so as to cover the opening, thereby forming a sealed container in which the luminous body is sealed. and forming step, a exposing step of exposing a dense closed container which has passed through the shape formed step in oxygen, while moving the photon counting unit along the oxygen barrier body, the photon count step of detecting the photon number M from light emission body when a determination step of determining whether or not the optical child number M exceeds the threshold value N, if it is determined that the "M>N" in determine the constant process, photon count upon detecting the number of photons M A position detecting step for detecting the position of the part.

It is preferable that a condensing lens is provided between the oxygen barrier and the photon counting unit so that the focal point is positioned on the photon counting entrance window. The forming step is preferably performed in a glove box filled with an inert gas.

  According to the present invention, since photons generated by chemiluminescence are counted to detect defects in the oxygen barrier body, a defect inspection of a high oxygen barrier body can be performed with high accuracy. Furthermore, since chemiluminescence takes a short time from the oxidation reaction until photons are generated, defect inspection can be performed in a short time.

It is a perspective view which shows the outline | summary of a 1st oxygen permeable amount measuring apparatus. It is a perspective view which shows the outline | summary of the airtight container provided in a 1st oxygen permeable amount measuring apparatus. It is an exploded view which shows the outline | summary of an airtight container. It is sectional drawing which shows the outline | summary of a 1st oxygen permeable amount measuring apparatus. It is a perspective view which shows the outline | summary of the 2nd oxygen permeable amount measuring apparatus. It is a perspective view which shows the outline | summary of the 3rd oxygen permeable amount measuring apparatus. It is sectional drawing which shows the outline | summary of the 4th oxygen permeable amount measuring apparatus.

  A defect detection apparatus 10 of the present invention is shown in FIG. The defect detection apparatus 10 includes a sealed container 13 containing a light emitter 12 and a photon counter 15 provided in the vicinity of the sealed container 13. The sealed container 13 has an oxygen barrier property.

  As shown in FIGS. 2 and 3, the sealed container 13 includes a box-shaped vessel 17 in which a luminescent material that emits chemiluminescence by an oxidation reaction is disposed, and an oxygen barrier film 18 that is a target for defect inspection. The vessel 17 has an opening 17a, and a support surface 17b for supporting the oxygen barrier film 18 is provided on the periphery of the opening 17a.

The oxygen barrier film 18 is light transmissive. The oxygen permeability of the oxygen barrier film 18 ^is preferably from ^{10 -2 ~10 -6 (cc / m} 2 · day · atm), 10 -2 ~10 -3 (cc / m 2 · day · atm) It is more preferable that

  A vessel 17 having a lower oxygen permeability than the oxygen barrier film 18 is used. For example, it is preferably made of glass or one having the same oxygen permeability. The shape, dimensions, and the like of the opening 17a are not limited as long as the opening 17a can be closed by the oxygen barrier film 18, and the closed container 13 can be in a sealed state by closing the opening 17a.

  When the oxygen barrier film 18 is disposed on the container 17 so as to close the opening 17a, the luminescent material disposed in the container 17 is sealed as shown in FIG. Thus, the light emitter 12 made of the light emitting material is formed in the sealed container 13.

  Examples of the method of arranging the luminescent substance in the vessel 17 include a method of spreading droplets by using a blade after dropping a droplet, a single wafer applied by moving a blade, a wire bar, a hopper, etc. in parallel to a horizontally fixed substrate. A coating apparatus, a spin coating apparatus that rotates while holding the substrate horizontally, and the like can be used, but are not limited thereto.

  As a method for sealing the luminescent substance in the vessel 17, after applying a sealing agent such as EVA to the support surface 17 b of the vessel 17, the oxygen barrier film 18 is pressure-bonded. At this time, the coating width of the sealing agent is 1 cm or more. The oxygen barrier film and the luminescent material are closely attached so that no gas (in this case, an inert gas in the glove box) remains. When the inspection region is a part of the bottom surface of the vessel, the gas between the oxygen barrier film and the luminescent material may be left outside the inspection region even if it remains.

  The chemiluminescent substance of the present invention represents a substance that emits a photon by a reaction with oxygen, and examples thereof include a compound having a double bond substituted with an electron donating group and an oil and fat having an unsaturated bond. A compound having a double bond substituted with an electron donating group is preferable from the viewpoint of light emission, and a compound having a structure represented by the general formula (1) is particularly preferable.

In the general formula shown in Chemical Formula 1, each of R ₁ to R ₈ represents an independent alkyl group and may be linked to each other to form a ring.

The alkyl group represented by R ₁ to R ₈ is a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms. As the substituent, for example, an alkoxy group ( Preferably 1 to 4 carbon atoms, such as methoxy, ethoxy, 2-methylpropoxy), acyl groups (preferably 2 to 4 carbon atoms such as acetyl, butyroyl, pivaloyl), acyloxy groups (preferably 2 to 4 carbon atoms such as Acetoxy, butyroyloxy, pivaloyloxy) and halogen atoms (for example, F, Cl, Br, I) may be contained. The cyclic alkyl group represented by R ₁ to R ₈ is preferably a 4- to 7-membered ring, particularly preferably a 5- or 6-membered ring. The ring formed by connecting alkyl groups represented by R ₁ to R ₈ to each other is preferably a 4- to 8-membered ring, particularly preferably a 5- or 6-membered ring.

Among the compounds represented by Chemical formula 1, particularly preferred are those in which the alkyl groups represented by R ₁ to R ₈ are each independently an unsubstituted alkyl group having 1 to 2 carbon atoms. Further, among these unsubstituted alkyl groups having 1 to 2 carbon atoms, R ₂ and R ₃ , R ₆ and R ₇ may be linked to form a 5- or 6-membered ring.

Most preferred among the compounds represented by Chemical formula ₁ is that the alkyl group represented by R ₁ to R ₈ is a methyl group. Specific examples (compounds 1 to 16) of the compound represented by the general formula (1) are shown below, but the scope of the present invention is not limited thereto.

  Compound 16 is a compound shown in Chemical formula 3.

  The compound shown in Chemical Formula 1 can be synthesized by a known method described in the following non-patent literature. For example, compounds 1 to 8 can be obtained from RL Pruett, JT Barr, KE Rapp, CT Bahner, JD Gibson, RH Lafferty, Jr., J. Am. Chem. Soc., 72, 3646-3650 (1950) and N. Wieberg and JW Buchler, Z. Naturforsch, 196, 5-8 (1964). Compounds 9 to 16 can be synthesized based on the description of H. E. Winberg, J. E. Carnahan, D. D. Coffman, M. Brown, J. Am. Chem. Soc., 87, 2055-2056 (1965).

Explaining the mechanism of the luminescent reaction of the present invention as an example the reaction of tetrakis (the di main Chiruamino) ethylene (Compound 1) and oxygen. By reaction tetrakis (the di main Chiruamino) ethylene (Compound 1) with oxygen, 4 (see Formula 5 and Formula 6) tetramethylurea two molecules via a dioxetane shown in reduction is produced. Tetramethylurea shown in Chemical formula 6 is in an excited state. When tetramethylurea shown in Chemical Formula 6 transitions to the ground state, photons having energy corresponding to the energy difference between the excited state and the ground state are emitted. According to HE Winberg, JR Downing, DD Coffman, J. Am. Chem. Soc., 87, 2054-2055 (1965), the quantum yield of this reaction was 3 × 10 ⁻⁴ , which contributed to the reaction. Photons are generated at a rate of 2.5 to 3.4 (hereinafter referred to as a reaction rate) κ for 10,000 oxygen molecules.

  As shown in FIG. 4, the photon counter 15 that counts the number of photons is attached to the moving device 30. The moving device 30 includes a movable holder 31 and a drive unit 32 that moves the holder 31 in a predetermined direction. Since the photon counter 15 is attached to the holder 31, the photon counter 15 is movable.

  The photon counter 15 includes a photomultiplier tube including an incident window 15a through which photons can enter, and a counter module that counts the number of photons incident from the incident window 15a based on the pulse current value output from the photomultiplier tube. . The photon counter 15 disposed outside the sealed container 13 is disposed such that the incident window 15 a faces the oxygen barrier film 18. The quantum efficiency Qe of the photomultiplier tube is preferably 1 to 20%.

  The controller 35 reads the number of photons counted by the counter module from the photon counter 15. Further, the controller 35 reads the position of the holder 31 from the drive unit 32. Furthermore, the controller 35 drives the drive unit 32 based on the route information recorded in the built-in memory. Under the control of the controller 35, the holder 31 moves on the path from the movement start point to the movement end point. The movement start point, the movement end point, and the path from the movement start point to the movement end point are recorded in advance in the built-in memory of the controller 35.

  Next, a procedure for defect inspection of the oxygen barrier film 18 using the defect detection apparatus 10 will be described.

First, a vessel 17, a sealed bottle containing a luminescent material, and an oxygen barrier film 18 are placed in a glove box filled with an inert gas (see FIG. 3). As the inert gas, in addition to a rare gas, a low reactivity such as nitrogen can be used.

  In the glove box, the luminescent material is taken out from the sealed bottle and applied to the vessel 17. Thereafter, the oxygen barrier film 18 is bonded to the container 17 so that the opening 17a is closed. Thereby, the luminescent substance in the container 17 is sealed, and the light emitter 12 is formed inside the sealed container 13 (see FIG. 4). Then, the sealed container 13 is put in a sealed trunk case for transportation and taken to a dark room.

  The darkroom is filled with a gas containing oxygen (for example, air). The environmental conditions such as the temperature and humidity in the darkroom may be any conditions that cause the reaction of the luminescent material.

  A moving device 30 is arranged in the darkroom. The photon counter 15 is attached to the holder 31. In the dark room, the sealed container 13 is taken out from the sealed trunk case for transportation. At this time, the sealed container 13 is disposed so that the incident window 15a of the photon counter 15 disposed in the dark room and the oxygen barrier film 18 face each other close to 1 cm or less.

  The controller 35 sets the photon counter 15 at the movement start point. Next, the controller 35 reads holder position coordinates indicating the position of the holder 31 from the drive unit 32. Thereafter, the controller 35 determines whether or not the read holder position coordinate matches the coordinate of the movement end point recorded in the built-in memory. If the read holder position coordinates do not coincide with the coordinates of the movement end point, the controller 35 moves the holder 31 according to the route recorded in the built-in memory. As described above, the controller 35 moves the holder 31 until the read holder position coordinates coincide with the coordinates of the movement end point. Thus, the photon counter 15 set at the movement start point moves along the surface 18f of the oxygen barrier film 18 on a predetermined path to the movement end point.

  Oxygen in the dark room passes through the oxygen barrier film 18 and touches the luminescent material disposed inside the sealed container 13, but the defective part has a fast oxygen penetration time and a large amount of penetration, so in the initial stage of measurement. Only the defects glow brightly. Photons emitted from the defect enter the incident window 15 a of the photon counter 15. When a photon is incident from the incident window 15a, the photomultiplier tube outputs a predetermined pulse current according to the photon.

  The counter module reads the number of pulses and the current value output from the photomultiplier tube. Then, the number of photons incident on the incident window 15a is detected from the read pulse number and current value. Furthermore, the number M (number / second) of oxygen molecules that have passed through the oxygen barrier film 18 is calculated from the number of detected photons and the reaction rate κ.

  The controller 35 reads the number of oxygen molecules M (number / second) from the photon counter 15. Thereafter, the controller 35 records oxygen amount information in which the holder position coordinate and the number M of oxygen molecules are paired in the built-in memory. Next, the controller 35 determines whether or not the number M of oxygen molecules is larger than a threshold value N preset in the built-in memory. The threshold value N may be determined based on the oxygen permeability required for the oxygen barrier film 18 to be inspected.

  If it is determined that “M> N”, the controller 35 adds defect data to the oxygen amount information for the oxygen molecular weight M, and then records the next oxygen amount information in the built-in memory. On the other hand, when it is determined that “M <N” or “M = N”, the controller 35 records the next oxygen amount information in the built-in memory without adding defect data to the oxygen amount information.

  When the oxygen barrier film 18 has a defect, the number M of oxygen molecules in the defect is larger than the threshold value N. Therefore, the presence / absence of a defect in the oxygen barrier film 18 and the position of the defect can be specified from the oxygen amount information recorded in the built-in memory of the controller 35. Thus, since this invention detects a defect using the photon number emitted by oxidation, it can test a defect about the oxygen barrier film 18 at a faster speed than before.

  In the above embodiment, the luminescent material is arranged on the entire bottom surface of the vessel 17, but the present invention is not limited to this, and if the luminescent material is arranged in the range to be inspected, the luminescent material is arranged on the entire bottom surface. It does not have to be.

  In the above embodiment, the vessel 17 having the opening 17a and the support surface 17b is used. However, the present invention is not limited to this, and a plate may be used instead of the vessel 17. When a luminescent material is provided on a flat plate, the oxygen barrier film 18 may be pressure-bonded after applying a sealing material around the luminescent material on the flat plate.

  In the said embodiment, although the oxygen barrier film 18 which has a light transmittance was used, you may use the oxygen barrier film 18 which has a low light transmittance, or does not have a light transmittance. In this case, a photon counter 15 provided so as to be close to the back surface of the device 17 may be used to detect photons through the light-transmitting device 17.

  In the above embodiment, the sealed container 13 is taken out from the transport trunk case in the dark room, but the present invention is not limited to this. After the photon counter 15 is arranged inside or outside the glove box in the dark room, The atmosphere may be replaced.

  In the above embodiment, one photon counter 15 is used as the photon detector, but the present invention is not limited to this, and array type photon counters 40 and 42 as shown in FIGS. 5 and 6 may be used. The array type photon counter 40 shown in FIG. 5 has a plurality of photon counters 15 arranged. As shown in FIG. 6, when the photon counter 15 constituting the array photon counter 42 is arranged on the entire surface of the oxygen barrier film 18, the moving device 30 (see FIG. 4) can be omitted.

  Further, as shown in FIG. 7, a condensing lens 45 may be provided between the photon counter 15 and the oxygen barrier film 18. It is preferable that the condensing lens 45 is arranged so that the focal point is located in the incident window 15a. Thereby, the specific precision of a position about the defect of the oxygen barrier film 18 can be improved.

  Although the photomultiplier tube is used in the above embodiment, the present invention is not limited to this, and a CCD image sensor with an image intensifier may be used. In this case, it becomes a photon accumulation type integral measurement.

A defect inspection was performed on the oxygen barrier material using the defect detection apparatus 10 shown in FIG. The oxygen barrier material is obtained by stacking a metal plate having fine holes on a base film. The oxygen permeability in the portion of the oxygen barrier material provided with the fine holes was 20 cc / day · m ² · atm. The number of photons detected at 4 hours after the defect detection apparatus 10 was placed in the dark room was 10 / second in most parts of the oxygen barrier material, whereas 77 / Second. Further, the portion where the number of photons was detected as 77 / sec coincided with the position where the fine holes were provided. Therefore, according to the present invention, it has been found that a minute defect can be detected, and further, such a minute defect can be detected in a short time.

DESCRIPTION OF SYMBOLS 10 Defect detection apparatus 12 Luminous body 13 Sealed container 15 Photon counter 17 Support box 18 Oxygen barrier film 30 Moving apparatus 31 Holder 32 Drive part 35 Controller 40, 42 Array type photon counter

Claims (8)

In the oxygen barrier body defect detection apparatus for detecting defects in the film-like oxygen barrier body using chemiluminescence by oxidation,
A box-shaped vessel having an opening and a support surface at the periphery of the opening, and a vessel that forms a sealed space by adhering the oxygen barrier body to the support surface so as to cover the opening;
A light emitter that is arranged in the sealed space so as to spread toward the opening, and causes the chemiluminescence;
Photon counting unit for detecting the number of photons M from the light emitter move along the front-hexane containing barrier body,
A determination unit for determining whether or not the photon number M exceeds a threshold N;
A defect in an oxygen barrier body, comprising: a position detection unit that detects a position of the photon counting unit when the number M of photons is detected when the determination unit determines that “M> N”. Detection device. 2. The oxygen barrier body according to claim 1, further comprising a condensing lens provided between the oxygen barrier and the photon counting unit and arranged so that a focal point is located on an entrance window of the photon counting. Defect detection device. The defect detection apparatus for an oxygen barrier body according to claim 1 or 2, wherein the apparatus is a glove box filled with an inert gas, and has a glove box that provides a space for forming the sealed space. The defect detection apparatus for an oxygen barrier body according to any one of claims 1 to 3, further comprising a photon detection array in which the photon counting units are arranged. Wherein the light emitter, tetrakis (di main Chiruamino) defect detection apparatus of the oxygen barrier material according to any one of to no claim 1, characterized in that included ethylene 3. In the oxygen barrier body defect detection method for detecting defects in a film-like oxygen barrier body using chemiluminescence by oxidation,
For a box-shaped vessel having an opening and a support surface at the peripheral edge of the opening, a luminous body that causes the chemiluminescence is spread in the vessel so as to cover the opening. Forming the sealed container in which the light emitter is sealed by bonding the oxygen barrier body to the support surface ;
An exposure step of exposing the sealed container that has undergone the forming step to oxygen ;
While moving the photon counting unit along said oxygen barrier material, and photon counts step of detecting the photon number M from the light emitter,
A determination step of determining whether or not the number of photons M exceeds a threshold N;
A defect of an oxygen barrier body, comprising: a position detection step of detecting a position of the photon counting unit when the photon number M is detected when it is determined that “M> N” in the determination step. Detection method. The defect detection of the oxygen barrier body according to claim 6, wherein a condensing lens is provided between the oxygen barrier and the photon counting unit so that a focal point is located on an incident window of the photon count. Method. The method for detecting a defect in an oxygen barrier body according to claim 6 or 7, wherein the forming step is performed in a glove box filled with an inert gas.

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