Laminate, manufacturing method thereof, and container for measurement

Abstract

To provide a laminate that can suppress scratches and foreign matter adhesion on a surface of a cycloolefin polymer film while inhibiting an increase in the autofluorescence, a manufacturing method of the laminate, and a container for measurement using the cycloolefin polymer film of the laminate.SOLUTION: A laminate having a cycloolefin polymer film used at the bottom of a container for measurement of a spectroscopic measuring device, has: the cycloolefin polymer film; and a protective film disposed on at least one surface of the cycloolefin polymer film, wherein the protective film has an adhesive layer that adheres to the cycloolefin polymer film, and the adhesive layer has an adhesive force to the cycloolefin polymer film that is equal to or less than a predetermined value.SELECTED DRAWING: Figure 4

Description

Technical Field

[0001] The present invention relates to a laminate having a cycloolefin polymer film used at the bottom of a measurement container of a spectroscopic measurement device, a method for manufacturing the same, and a measurement container of a spectroscopic measurement device.

Background Art

[0002] For example, in a measurement container of a spectroscopic measurement device such as a well plate, the bottom of the container may be formed using a resin film (Patent Documents 1 and 2). As such a resin film, for example, a cycloolefin polymer film is used because of its low autofluorescence.

[0003] Although not related to the resin film used for the measurement container, Patent Document 3 describes laminating a protective film on an optical film for protecting optical films such as a retardation film and a polarizing film.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] In a spectroscopic measurement device, spectroscopic measurement of a sample in a measurement container is performed through the bottom of the measurement container. Therefore, in the measurement container of the spectroscopic measurement device, if there are scratches on the surface of the cycloolefin polymer film or foreign substances are attached thereto, there is a risk of inhibiting the measurement of the sample. Therefore, when storing and transporting the cycloolefin polymer film, it is desirable to dispose a protective film on the surface of the cycloolefin polymer film. However, when a protective film is disposed, the autofluorescence of the cycloolefin polymer film may increase (the autofluorescence may deteriorate).

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a laminate capable of suppressing an increase in autofluorescence while suppressing scratches on the surface of a cycloolefin polymer film and adhesion of foreign substances, a method for producing the same, and a measurement container using the cycloolefin polymer film of the laminate.

Means for Solving the Problems

[0007] The present inventor has found that an increase in autofluorescence is caused by the components of the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer of the protective film remaining on the cycloolefin polymer film. The present invention has been made based on the above finding. The present invention is as follows.

[0008] 〔1〕 A laminate having a cycloolefin polymer film used at the bottom of a measurement container of a spectroscopic measurement device, the laminate having the cycloolefin polymer film and a protective film disposed on at least one surface of the cycloolefin polymer film, the protective film having a pressure-sensitive adhesive layer that adheres to the cycloolefin polymer film, and the pressure-sensitive adhesive layer having an adhesive force to the cycloolefin polymer film of 0.5 N or less. 〔2〕 The laminate according to 〔1〕, wherein the thickness of the cycloolefin polymer film is 20 μm or more and 300 μm or less. 〔3〕The laminate according to 〔1〕 or 〔2〕, wherein the cycloolefin polymer film has a rectangular shape and the ratio of the short side to the long side is 1 / 2 or more and less than 1. 〔4〕The laminate according to any one of 〔1〕 to 〔3〕, wherein the ratio of the thickness of the protective film to the thickness of the cycloolefin polymer film is 1 / 10 or more and 1 / 2 or less. 〔5〕The laminate according to any one of 〔1〕 to 〔4〕, wherein the protective film is in a long strip shape and a plurality of the cycloolefin polymer films are arranged in series in the plane direction of the protective film. 〔6〕A method for manufacturing a laminate, which is a method for manufacturing the laminate according to 〔5〕, including a step A of bonding a cycloolefin polymer film and a protective film, and a step B of cutting the cycloolefin polymer film bonded to the protective film, removing unnecessary portions, and arranging a plurality of the cycloolefin polymer films in series in the plane direction of the protective film. 〔7〕A measurement container for a spectroscopic measurement device, which is a measurement container formed using the cycloolefin polymer film of the laminate according to any one of 〔1〕 to 〔4〕. 〔8〕The measurement container according to 〔7〕, wherein the measurement container is a well plate.

Advantages of the Invention

[0009] According to the laminate of the present invention, since the adhesive layer of the protective film has a predetermined adhesive force, it is possible to provide a laminate capable of suppressing scratches on the surface of the cycloolefin polymer film and adhesion of foreign substances, while suppressing an increase in autofluorescence, a method for manufacturing the same, and a measurement container using the cycloolefin polymer film of the laminate.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Mode for Carrying Out the Invention

[0011] Hereinafter, the present invention will be described in detail with reference to embodiments and exemplifications. However, the present invention is not limited to the embodiments and exemplifications shown below, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope. The components of the embodiments shown below can be appropriately combined. Also, the existing reference numerals in the drawings may be omitted.

[0012] In the following description, "long" refers to a shape having a length that is usually 5 times or more the width, preferably 10 times or more the length, and specifically, a shape having a length such that it can be wound up and stored or transported in a roll shape. The upper limit of the ratio of the length to the width is not particularly limited, but can be, for example, 100,000 times or less.

[0013] In the following description, "rectangular" refers to a shape having a length that is usually less than 5 times the width.

[0014] In the following description, unless otherwise specified, the "layer" and the "film" may be a flexible member such as a resin film, or a rigid member.

[0015] In the following description, when a member is "directly" disposed on another member, unless otherwise specified, it means that the two members are in contact with each other and there is no other member between the two members.

[0016] In the following description, the cycloolefin polymer film refers to a film containing a cycloolefin polymer. In the following description, the cycloolefin polymer film may be described as a "COP film".

[0017] [1. Overview of the laminate] The laminate according to an embodiment of the present invention has a COP film used at the bottom of a measurement container of a spectroscopic measurement device. This laminate has a COP film and a protective film disposed on at least one surface of the COP film. This protective film has an adhesive layer that adheres to the COP film. The adhesive layer has an adhesive force to the COP film that is equal to or less than a predetermined value.

[0018] FIGS. 1 and 2 are cross-sectional views schematically showing an example and another example of a laminate 10 according to an embodiment of the present invention. In FIG. 1, a laminate 10A in which a protective film 2 is disposed on one side of a COP film 1 is shown, and in FIG. 2, a laminate 10B in which protective films 2a and 2b are disposed on both sides of the COP film 1, respectively, is shown.

[0019] As shown in Fig. 1, the laminate 10A has a COP film 1 and a protective film 2 disposed on one surface of the COP film 1. In the laminate 10A, the protective film 2 has an adhesive layer 21 that adheres to the COP film 1. As shown in Fig. 1, the protective film 2 is usually disposed directly on the surface of the COP film 1, and the adhesive layer 21 of the protective film 2 is in close contact with the surface of the COP film 1. In Fig. 1, an example in which the protective film 2 includes an adhesive layer 21, a base material layer 22, and a back layer 23 is shown, but the present invention is not limited thereto. In the laminate 10A, the adhesive layer 21 has an adhesive force to the COP film 1 that is equal to or less than a predetermined value.

[0020] As shown in Fig. 2, the laminate 10B has a protective film 2a and a protective film 2b on both surfaces of the COP film 1, respectively. In Fig. 2, an example is shown in which a protective film 2a including an adhesive layer 21a, a base material layer 22a, and a back layer 23a is disposed directly on one surface of the COP film 1, and a protective film 2b including an adhesive layer 21b, a base material layer 22b, and a back layer 23b is disposed directly on the other surface of the COP film 1. When the laminate 10B has the protective film 2a and the protective film 2b on both surfaces of the COP film 1, respectively, usually, in both the adhesive layer 21a and the adhesive layer 21b, the adhesive force to the COP film 1 is equal to or less than a predetermined value.

[0021] According to the present embodiment, since the adhesive layer of the protective film is disposed in close contact with the surface of the COP film, it is possible to prevent the surface of the COP film from being scratched or foreign matters from adhering thereto. On the other hand, since the components of the adhesive contained in the adhesive layer usually emit autofluorescence, if the components of the adhesive remain on the surface of the COP film, the autofluorescence of the COP film may increase. In contrast, according to the laminate according to the present embodiment, since the adhesive force of the adhesive layer of the protective film to the COP film is not too high, the protective film can be easily peeled off from the COP film, and the remaining of the components of the adhesive on the surface of the COP film can be suppressed. Therefore, an increase in the autofluorescence of the COP film can be suppressed.

[0022] [2. COP Film] The COP film according to this embodiment is a film used at the bottom of a measurement container of a spectroscopic measurement device.

[0023] The COP film is a film containing a cycloolefin polymer. The cycloolefin polymer represents a polymer having a structure obtained by polymerizing a cycloolefin monomer. Further, the cycloolefin monomer represents a compound having a ring structure formed of carbon atoms and having a polymerizable carbon-carbon double bond in the ring structure. Examples of the polymerizable carbon-carbon double bond include carbon-carbon double bonds capable of polymerization such as ring-opening polymerization. Examples of the ring structure of the cycloolefin monomer include monocyclic, polycyclic, condensed polycyclic, bridged ring, and polycyclic combinations thereof.

[0024] The cycloolefin polymer preferably contains an alicyclic structure as the above ring structure in the repeating unit. Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure. From the viewpoint of thermal stability, a cycloalkane structure is preferred. The number of carbon atoms contained in one alicyclic structure is preferably 4 or more, more preferably 5 or more, particularly preferably 6 or more, preferably 30 or less, more preferably 20 or less, particularly preferably 15 or less.

[0025] In the cycloolefin polymer, the proportion of the repeating unit containing an alicyclic structure is preferably 50% by weight or more, more preferably 70% by weight or more, particularly preferably 90% by weight or more. When the proportion of the repeating unit containing an alicyclic structure is within the above range, a COP film excellent in heat resistance can be obtained.

[0026] Preferred examples of the cycloolefin polymer include norbornene-based polymers, monocyclic cyclic olefin-based polymers, cyclic conjugated diene-based polymers, and hydrides thereof. Among these, norbornene-based polymers and their hydrides have good transparency and moldability.

[0027] Examples of the norbornene polymer and its hydride include ring-opening polymers of monomers having a norbornene structure and their hydrides; addition polymers of monomers having a norbornene structure and their hydrides. Examples of the ring-opening polymer of a monomer having a norbornene structure include ring-opening homopolymers of one type of monomer having a norbornene structure, ring-opening copolymers of two or more types of monomers having a norbornene structure, and ring-opening copolymers of a monomer having a norbornene structure and any monomer copolymerizable therewith. Further, examples of the addition polymer of a monomer having a norbornene structure include addition homopolymers of one type of monomer having a norbornene structure, addition copolymers of two or more types of monomers having a norbornene structure, and addition copolymers of a monomer having a norbornene structure and any monomer copolymerizable therewith. Examples of these polymers include polymers disclosed in, for example, JP-A-2002-321302.

[0028] Specific examples of the norbornene polymer and its hydride include "Zeonex" manufactured by Nippon Zeon Co., Ltd.; "Arton" manufactured by JSR Corporation; "TOPAS" manufactured by TOPAS ADVANCED POLYMERS.

[0029] The thickness of the COP film is appropriately selected according to the measuring container in which the COP film is used. Usually, it is 20 μm or more, preferably 50 μm or more, more preferably 70 μm or more, and usually 300 μm or less, more preferably 250 μm or less, and even more preferably 200 μm or less. This is because when the thickness of the COP film is within the above range, the sample can be held and analyzed well when used in the measuring container.

[0030] Since the COP film is usually used by transmitting light such as excitation light and detection light at the bottom of the measurement container, it is preferably transparent. Therefore, it is preferable that the total light transmittance of the COP film is high. The specific total light transmittance of the COP film is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. The total light transmittance can be measured in the wavelength range of 400 nm to 700 nm using an ultraviolet-visible spectrometer.

[0031] The COP film may be in a long strip shape or may have a single-sheet shape. When the COP film has a single-sheet shape, the specific shape is not particularly limited as long as it can form the bottom of the measurement container, but a rectangular shape is preferable. When the COP film is rectangular, the corners may or may not have rounding (R).

[0032] As shown in FIG. 3, when the COP film 1 is rectangular, the ratio (S2 / S1) of the length S2 of the short side to the length S1 of the long side is usually greater than 0.20, preferably 1 / 2 (0.5) or more, more preferably 0.6 or more, and even more preferably 0.65 or more. Also, the ratio (S2 / S1) is usually less than 1, preferably 0.9 or less, and more preferably 0.8 or less. This is because when the ratio (S2 / S1) is within the above range, it is easy to use as the bottom of the measurement container.

[0033] The specific size of the rectangular COP film can be appropriately selected according to the type and size of the measurement container. For example, when the COP film is used at the bottom of a well plate, the length of the long side is usually 100 mm or more, preferably 105 mm or more, and usually 125 mm or less, preferably 120 mm or less. Also, the length of the short side is usually 60 mm or more, preferably 70 mm or more, and usually 90 mm or less, preferably 80 mm or less.

[0034] 〔3. Protective Film〕 The protective film is disposed on at least one surface of the COP film and is used to prevent scratches, dirt, etc. from occurring on the surface of the COP film.

[0035] In the laminate, the protective film may be disposed on one side of the COP film or on both sides of the COP film. From the viewpoint of protecting the COP film, it is preferably disposed on both sides of the COP film.

[0036] The protective film usually has an adhesive layer for adhering to the COP film. The adhesive force of the adhesive layer to the COP film is usually 0.5 N or less, preferably 0.4 N or less, more preferably 0.35 N or less. Also, the adhesive force can usually be 0.01 N or more, preferably 0.02 N or more, more preferably 0.03 N or more. When the adhesive force of the adhesive layer of the protective film is below the above upper limit value, the remaining components of the adhesive on the COP film can be effectively suppressed, so the increase in self-luminescence can be effectively suppressed. On the other hand, when the adhesive force of the adhesive layer of the protective film is above the above lower limit value, the adhesion between the COP film and the protective film can be sufficiently ensured, so scratches and foreign matter adhesion on the COP film surface can be effectively suppressed by the protective film.

[0037] The adhesive force of the adhesive layer of the protective film to the COP film can be measured by performing a 180-degree peel test on the laminate. The 180-degree peel test can be carried out by cutting out the laminate into a rectangular test piece with a width of 50 mm and a length of 110 mm in the width direction, and peeling the protective film from the COP film from one end to the other end in the longitudinal direction of the test piece at a peeling speed of 100 m / min. As the evaluation instrument, for example, a high-performance digital force gauge ZTA-5N (manufactured by IMADA Co., Ltd.) can be used. The average value of the measurement results for three test pieces can be used as the adhesive force.

[0038] The protective film usually has an adhesive layer for adhering to the COP film. The protective film may further include a base material layer for supporting the adhesive layer, and, if necessary, a back layer disposed on the surface opposite to the adhesive layer side of the base material layer. The layer structure of the protective film may be, for example, two layers of an adhesive layer and a base material layer, or three layers of an adhesive layer, a base material layer, and a back layer. In this embodiment, among others, it is preferable that the protective film has an adhesive layer, a base material layer, and a back layer.

[0039] Examples of materials that can be used for the adhesive layer of the protective film include, for example, polyethylene. Examples of materials that can be used for the base material layer and the back layer of the protective film include, for example, polyethylene and polypropylene.

[0040] As the protective film, commercially available products may be used. Examples of commercially available products include "Toretec" (7531, 7111, 7232) manufactured by Toray Film Processing Co., Ltd.; "Esperan" manufactured by Okura Industries Co., Ltd.

[0041] The thickness of the protective film is not particularly limited as long as it can protect the surface of the COP film. For example, it is 20 μm or more, preferably 30 μm or more, more preferably 40 μm or more, and for example, 150 μm or less, preferably 100 μm or less, more preferably 80 μm or less. This is because when the protective film is within the above range, it can adhere well to the COP film, thereby effectively protecting the surface of the COP film. Also, it is because the protective film can be easily peeled off from the COP film.

[0042] In the laminate, considering the balance between the ease of protecting the surface of the COP film with the protective film and the ease of peeling the protective film from the surface of the COP film, it is preferable that the ratio of the thickness of the protective film to the thickness of the COP film is within a predetermined range. Specifically, as the ratio of the thickness of the protective film to the thickness of the COP film, it is preferably 1 / 10 (0.1) or more, more preferably 0.15 or more, particularly preferably 0.2 or more, and preferably 1 / 2 (0.5) or less, more preferably 0.45 or less, particularly preferably 0.40 or less. When the protective film is within the above range, the surface of the COP film can be well protected by the protective film, and the protective film can be easily peeled from the COP film.

[0043] The ratio of the thickness of the protective film to the thickness of the COP film refers to the ratio (T2 / T1) of the distance T2 in the thickness direction of the protective film 2 to the distance T1 in the thickness direction of the COP film 1 in the laminate 10A shown in FIG. 1. Also, as shown in FIG. 2, when the laminate 10B has the protective film 2a and the protective film 2b on both surfaces of the COP film 1, the ratio (T2a / T1) of the distance T2a in the thickness direction of the protective film 2a to the distance T1 in the thickness direction of the COP film 1, and the ratio (T2b / T1) of the distance T2b in the thickness direction of the protective film 2b to the distance T1 in the thickness direction of the COP film 1 are each referred to. In the laminate 10B shown in FIG. 2, it is preferable that both the ratio (T2a / T1) and the ratio (T2b / T1) are within the above-mentioned range.

[0044] The shape of the protective film may be any shape that can protect the surface of the COP film, and it may be in a long shape or may have a single-sheet shape, but it is preferably in a long shape.

[0045] 〔4. Form of the laminate〕 As the form of the laminate according to the present embodiment, for example, it may be a long laminate or a single-sheet laminate, but a long laminate is more preferable. This is because a long laminate can be manufactured efficiently.

[0046] When the laminate is in a long shape, for example, it can take a form in which a long COP film and a long protective film are laminated.

[0047] Also, when the laminate is in a long shape, for example, the protective film can be in a long shape, and a plurality of COP films can be arranged in a row in the plane direction of the protective film. As an example, like the laminate 10C shown in FIG. 4, on the surface of a single long protective film 2, a plurality of sheet-like COP films 1a to 1e can be arranged side by side in the longitudinal direction of the protective film 2. In this form, since the COP film can be arranged on the protective film in a state where it has been previously cut out into a shape that fits the bottom of the measuring container, the production of the measuring container can be facilitated.

[0048] When the laminate is in a long shape, it is usually stored and transported as a roll body wound in a roll shape.

[0049] 〔5. Method for manufacturing laminate〕 The laminate according to the present invention can usually be manufactured by a manufacturing method including a step of bonding a COP film and a protective film. Preferred examples of the manufacturing method of the laminate include a manufacturing method having the following steps A and B. Step A: A step of bonding a COP film and a protective film. Step B: A step of making a cut in the COP film bonded to the protective film, removing unnecessary portions, and arranging a plurality of COP films in a row in the plane direction of the protective film.

[0050] Hereinafter, the manufacturing method of the laminate including steps A and B will be described as the manufacturing method of the laminate according to an embodiment of the present invention. The laminate obtained by bonding the COP film and the protective film in step A is also a configuration included in the laminate according to the present invention, but in order to distinguish it from the laminate obtained in step B, in the following description, the laminate obtained in step A will be described as a bonded body.

[0051] FIG. 5 is a process diagram showing an example of a method for manufacturing a laminate according to an embodiment of the present invention. In step A, as shown in FIG. 5(a), a COP film 1 and a protective film 2 (protective film 2a) are bonded together. Thereby, a bonded body 11 can be obtained. Next, in step B, as shown in FIG. 5(b), for example, by performing press working using a die D, a cut is made in the COP film 1 bonded to the protective film 2a. At this time, so-called half-cut processing may be performed in which the protective film 2a is also cut halfway in the thickness direction. Next, unnecessary portions of the COP film 1 from the bonded body 11 (in FIG. 5(b), the COP film 1 located at the end of the bonded body 11) are removed. Thereby, as shown in FIG. 5(c), a COP film 1 having a desired shape remains on the surface of the protective film 2a. By performing steps A and B in this way, since a plurality of COP films 1 can be arranged continuously in the plane direction of the protective film 2a, for example, the laminate 10C shown in FIG. 4 described above can be manufactured. In the present embodiment, if necessary, as shown in FIG. 5(d), a step of arranging another protective film 2b on the surface of the COP film 1 opposite to the surface on which the protective film 2a is arranged may be included. Thereby, the laminate 10D can be manufactured.

[0052] FIG. 6 is a process diagram showing another example of a method for manufacturing a laminate according to an embodiment of the present invention. In FIG. 6, an example of manufacturing the laminate according to the present embodiment using a roll-to-roll method is shown. In the example shown in FIG. 6, first, a long COP film 1 wound in a roll shape and a long protective film 2a wound in a roll shape are prepared. Next, in step A, the long COP film 1 and the long protective film 2a are bonded to form a long bonded body 11. Next, in step B, a die D is pressed from the side of the COP film 1 of the long bonded body 11 to cut the COP film 1, and unnecessary portion 1u is removed, and a plurality of COP films 1 are arranged continuously in the surface direction of the protective film 2a to obtain a laminate 10C. Further, a long protective film 2b is bonded onto the surface of the laminate 10C on the side opposite to the protective film 2a of the COP film 1. Thereby, a laminate 10D in which the protective film 2a and the protective film 2b are arranged on both surfaces of the COP film 1 can be manufactured.

[0053] According to the method for manufacturing a laminate according to the present embodiment, by including step A and step B, it is possible to manufacture a laminate that can suppress an increase in autofluorescence while suppressing scratches and foreign matter adhesion on the surface of the COP film. Further, in this manufacturing method, since a plurality of COP films can be arranged continuously in the surface direction of the protective film, it is possible to manufacture a laminate that can efficiently manufacture a measurement container.

[0054] 〔5.1. Step A〕 Step A is a step of bonding a COP film and a protective film. In step A, usually, the adhesive layer of the protective film is brought into contact with at least one surface of the COP film to bond the COP film and the protective film. Examples of such bonding include, but are not limited to, a method of pressing the films together using a laminator device, and known bonding methods can be adopted.

[0055] In Process A, a sheet-like COP film and a sheet-like protective film may be laminated, or a long-strip COP film and a long-strip protective film may be laminated, but the latter is more preferable. Since a long-strip laminate can be manufactured by the roll-to-roll method and then used in the next process in the form of a roll, and the next process can also be carried out using the roll-to-roll method, the manufacturing efficiency is high and a laminate can be manufactured.

[0056] In Process A, a protective film may be laminated on at least one surface of the COP film, but from the viewpoint of protecting the COP film, it is preferable to laminate protective films on both surfaces of the COP film.

[0057] In Process A, if necessary, the long-strip laminate may be formed into a roll body wound in a roll shape. Also, slit processing may be performed in which the laminated sheet of the roll body is continuously cut into a certain width and then wound again.

[0058] 〔5.2. Process B〕 Process B is a process in which cuts are made in the COP film laminated on the protective film, unnecessary portions are removed, and a plurality of COP films are arranged continuously in the plane direction of the protective film.

[0059] In Process B, cuts are made in the COP film of the laminate obtained in Process A. When the laminate has protective films on both surfaces of the COP film, after peeling off one protective film, cuts are made in the COP film laminated on the protective film.

[0060] The method of making cuts in the COP film is not particularly limited, and any method that can obtain a plurality of COP films having a desired planar shape from a single COP film may be used. A preferable example is the die-cutting method using a die. When the die-cutting method is used, it is usually cut by applying a die to the COP film of the laminate and pressing. At this time, half-cut processing may be performed in which the cut is made up to the middle of the protective film.

[0061] After making incisions in the COP film, remove the unnecessary portions of the COP film. As a result, a plurality of COP films can be arranged in a row in the plane direction of the protective film.

[0062] 〔5.3. Optional process, etc.〕 In the method for manufacturing a laminate according to the present embodiment, after removing the unnecessary portions of the COP film in step B, it is preferable to have a step of laminating another protective film on the surface of the COP film opposite to the protective film side. This is because the surface of the COP film can be more effectively protected since one surface of the COP film is not exposed.

[0063] In the present embodiment, optionally, a step of cutting out a sheet-like laminate from the long laminate may be included.

[0064] The method for manufacturing a laminate according to the present embodiment is preferably carried out using a roll-to-roll method as shown in FIG. 6. This is because the laminate according to the present embodiment can be manufactured efficiently.

[0065] 〔6. Measuring container〕 The measuring container according to an embodiment of the present invention is a measuring container for a spectroscopic measuring device and is formed using the above-described COP film.

[0066] In a spectroscopic measuring device, generally, light is detected through the bottom of the measuring container to perform spectroscopic measurement of a sample in the container. According to the present embodiment, since it is formed using a COP film with suppressed scratches and foreign matter adhesion and low autofluorescence, it can be a measuring container capable of accurately measuring a sample.

[0067] The measuring container usually has a side surface portion and a bottom portion. Also, the COP film of the laminate described above is usually used for the bottom of the measuring container. In the measuring container, generally, the side surface portion and the bottom portion are integrally formed.

[0068] The side surface portion usually contains a resin including a polymer. As the polymer contained in the resin used for the side surface portion, known polymers that can be used for a measurement container can be used. Among them, from the viewpoint of improving the adhesion between the side surface portion and the bottom portion, it is preferable that the resin used for the side surface portion contains a cycloolefin polymer. The resin used for the side surface portion may be transparent or opaque. Further, the side surface portion may contain a known light-shielding material as necessary.

[0069] As a method for molding the measurement container, preferably, an insert molding method is used. As a method for manufacturing a measurement container using the insert molding method, for example, it may include a step of peeling the protective film from the laminate to separate the COP film, a step of inserting the COP film separated from the laminate into a mold, and a step of injecting and molding a resin into the mold to obtain a side surface portion integrated with the COP film.

[0070] As a type of the measurement container, it can be a known container that can hold a sample during measurement using a spectroscopic measurement device, and preferably it is a well plate. A well plate is also referred to as a microplate, and is an experimental instrument having a plurality of wells (depressions) on a flat plate and can also be used as a measurement container.

[0071] FIG. 7 is a perspective view schematically showing an example of a measurement container according to an embodiment of the present invention. In FIG. 7, an example in which the measurement container is a well plate is shown. As shown in FIG. 7, the measurement container (well plate) 30 has a side surface portion 31 located on the side surface of the well plate 30 and a bottom portion 32 located at the bottom of the well plate 30. The side surface portion 31 has holes h corresponding to the depressions of the well plate 30. In the well plate 30, usually, the COP film 10 is used for the bottom portion 32. In the well plate 30, usually, the side surface portion 31 and the bottom portion 32 are integrally formed.

[0072] In the well plate 30 shown in FIG. 7, an example is shown in which 96 frustum-shaped holes h are arranged on the side surface in a ratio of 8:12, but the present invention is not limited to this. The shape and number of holes in the well plate can be appropriately selected according to the use of the well plate and the like.

[0073] The well plate may have a lid that covers the side surface and the bottom surface as needed.

[0074] The measurement container according to the present embodiment is used as a measurement container of a spectroscopic measurement device. The spectroscopic measurement device can usually be a measurement device using fluorescence spectroscopy. As an example, a spectrofluorometer that irradiates a measurement sample with excitation light such as ultraviolet light, detects fluorescence from the measurement sample, and performs qualitative and quantitative analysis based on the characteristics of the fluorescence wavelength can be mentioned. As another example, a fluorescence microscope that irradiates a measurement sample with excitation light such as ultraviolet light and observes the object by observing the fluorescence phenomenon from the measurement sample can be mentioned.

Example

[0075] Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples shown below, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[0076] In addition, the operations described below were performed under the conditions of normal temperature (23°C) and normal pressure (1 atm) unless otherwise specified.

[0077] [Evaluation method] (Measurement method of fluorescence characteristics) A cycloolefin polymer film (COP film) was laminated with a protective film to produce laminates for Examples and Comparative Examples. After storing at 30°C for 7 days, the protective film was peeled off from the laminate to obtain only the COP film. For this COP film, using a spectrofluorometer (product name "FP-8500", manufactured by JASCO Corporation), the fluorescence peak when light with an excitation wavelength of 365 nm was incident was measured. The maximum peak height at a detection wavelength of 405 nm to 410 nm was defined as the peak intensity. Next, a COP film without the protective film was prepared as a reference, and the peak intensity was measured in the same manner. The fluorescence characteristics were evaluated by calculating the ratio to the reference (COP film with the protective film peeled off / reference COP film). The closer the ratio to the reference is to 1, the less the increase in autofluorescence is indicated.

[0078] (Method for measuring adhesive strength) After laminating a COP film and a protective film to produce laminates for Examples and Comparative Examples, the adhesive strength was measured by a 180-degree peel test after storing at 30°C for 7 days. The shape of the test piece was a rectangle with a width of 50 mm and a length of 110 mm in the longitudinal direction. For each test piece, the protective film was peeled off from the COP film, and the peel strength was measured. A 180-degree peel test was performed at a peel rate of 100 m / min from the non-adhesive part of the protective film, and the peel was carried out so that the peel progressed from one end to the other end in the longitudinal direction of the test piece. As the evaluation instrument, a high-performance digital force gauge ZTA-5N (manufactured by IMADA) was used. The average value of the measurement results for three test pieces was obtained as the adhesive strength.

[0079] [Example 1] Pellets of norbornene resin (trade name "ZEONOR1600", manufactured by Zeon Corporation, Japan) were dried at 100 °C for 5 hours. The obtained pellets were supplied to an extruder, melted in the extruder, and then extrusion molded to produce a COP film with a thickness of 188 μm. The obtained COP film was cut into 75 mm × 110 mm. Next, two protective films (trade name "Toretec 7531", manufactured by Toray Film Processing Co., Ltd.) were prepared. The cut COP film was arranged continuously on the adhesive layer of the protective film, and then another protective film was placed with its adhesive layer facing the other surface of the COP film, and these were bonded together using a laminator to obtain a laminate. Using the obtained laminate, evaluations of fluorescence characteristics and adhesive strength were carried out.

[0080] [Example 2] Except for using norbornene resin (trade name "ZEONOR1430", manufactured by Zeon Corporation, Japan) instead of norbornene resin (trade name "ZEONOR1600", manufactured by Zeon Corporation, Japan), the same operations as in Example 1 were performed to manufacture and evaluate a laminate.

[0081] [Example 3] Except for using a protective film (trade name "Toretec 7111", manufactured by Toray Film Processing Co., Ltd.) instead of the protective film (trade name "Toretec 7531", manufactured by Toray Film Processing Co., Ltd.), the same operations as in Example 1 were performed to manufacture and evaluate a laminate.

[0082] [Example 4] Except for using a protective film (trade name "Toretec 7232", manufactured by Toray Film Processing Co., Ltd.) instead of the protective film (trade name "Toretec 7531", manufactured by Toray Film Processing Co., Ltd.), the same operations as in Example 1 were performed to manufacture and evaluate a laminate.

[0083] [Example 5] Except for bonding the protective film only on one side, the same operations as in Example 1 were performed to manufacture and evaluate a laminate.

[0084] [Example 6] Of the two protective films, one protective film (trade name "Toretec 7531", manufactured by Toray Film Processing Co., Ltd.) was used in place of the protective film (trade name "Toretec 7111", manufactured by Toray Film Processing Co., Ltd.), and the operation was carried out in the same manner as in Example 1 to produce and evaluate the laminate.

[0085] [Comparative Example 1] A laminate was produced and evaluated in the same manner as in Example 1, except that a protective film (trade name "Toretec 7461", manufactured by Toray Film Processing Co., Ltd.) was used instead of the protective film (trade name "Toretec 7531", manufactured by Toray Film Processing Co., Ltd.).

[0086] [Comparative Example 2] A laminate was produced and evaluated in the same manner as in Example 1, except that a protective film (trade name "Toretec 7571", manufactured by Toray Film Processing Co., Ltd.) was used instead of the protective film (trade name "Toretec 7531", manufactured by Toray Film Processing Co., Ltd.).

[0087] The results are shown in Tables 1 and 2. In the tables, the two protective films arranged in the laminate are represented as protective film 2a and protective film 2b, respectively. Also, the abbreviations in the tables are as follows. Thickness T1: Thickness of the COP film (μm) Thickness T2a: Thickness of the protective film 2a (μm) Thickness T2b: Thickness of the protective film 2b (μm) Thickness ratio (T2a / T1): Ratio of the thickness of the protective film 2a (μm) to the thickness of the COP film (μm) Thickness ratio (T2b / T1): Ratio of the thickness of the protective film 2b (μm) to the thickness of the COP film (μm) Fluorescence characteristics: Ratio of the fluorescence peak intensity of the COP film with the protective film peeled off to the fluorescence peak intensity of the reference COP film Adhesion force (N / 50 mm): The average value of the measurement results of three test pieces in the 180-degree peel test described above. In Example 6 of Table 2, the adhesion force of the adhesive layer of the protective film 2a to the COP film (0.15 N / 50 mm) and the adhesion force of the adhesive layer of the protective film 2b to the COP film (0.06 N / 50 mm) are shown as "0.15 / 0.06".

[0088]

Table 1

[0089]

Table 2

[0090] As shown in Table 1 and Table 2, in the laminates of Examples 1 to 6 where the adhesion force is below a predetermined value, the increase in the autofluorescence of the COP film can be suppressed. However, in the laminates of Comparative Examples 1 and 2 where the adhesion force exceeds the predetermined value, the increase in the autofluorescence of the COP film could not be sufficiently suppressed.

Explanation of Reference Signs

[0091] 1, 1a, 1b, 1c, 1d, 1e: COP film 2, 2a, 2b: Protective film 10, 10A, 10B, 10C, 10D: Laminate 30: Measuring container (well plate) 31: Side surface part 32: Bottom part

Claims

1. A laminate having a cycloolefin polymer film used at the bottom of a measurement container of a spectroscopic measurement device, comprising the cycloolefin polymer film and a protective film disposed on at least one surface of the cycloolefin polymer film, wherein the protective film has an adhesive layer that adheres to the cycloolefin polymer film, and the adhesive layer has an adhesive force to the cycloolefin polymer film of 0.5 N or less.

2. The laminate according to claim 1, wherein the thickness of the cycloolefin polymer film is 20 μm or more and 300 μm or less.

3. The laminate according to claim 1, wherein the cycloolefin polymer film has a rectangular shape, and the ratio of the short side to the long side is 1 / 2 or more and less than 1.

4. The laminate according to claim 1, wherein the ratio of the thickness of the protective film to the thickness of the cycloolefin polymer film is 1 / 10 or more and 1 / 2 or less.

5. The laminate according to claim 1, wherein the protective film is long and a plurality of the cycloolefin polymer films are arranged in a row in the plane direction of the protective film.

6. A method for manufacturing a laminate, which is a method for manufacturing the laminate according to claim 5, comprising step A of bonding a cycloolefin polymer film and a protective film, and step B of cutting the cycloolefin polymer film bonded to the protective film, removing unnecessary portions, and arranging a plurality of the cycloolefin polymer films in a row in the plane direction of the protective film. A method for manufacturing a laminate including these steps.

7. A measurement container for a spectroscopic measurement device, which is formed using the cycloolefin polymer film of the laminate according to any one of claims 1 to 4.

8. The measurement container according to claim 7, wherein the measurement container is a well plate.

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