WO2022014374A1 - Procédé d'encapsulation - Google Patents

Procédé d'encapsulation Download PDF

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Publication number
WO2022014374A1
WO2022014374A1 PCT/JP2021/025134 JP2021025134W WO2022014374A1 WO 2022014374 A1 WO2022014374 A1 WO 2022014374A1 JP 2021025134 W JP2021025134 W JP 2021025134W WO 2022014374 A1 WO2022014374 A1 WO 2022014374A1
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WIPO (PCT)
Prior art keywords
methacrylate
polymer layer
acrylate
encapsulation
polymer
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PCT/JP2021/025134
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English (en)
Japanese (ja)
Inventor
健志 梅原
哲朗 三ツ井
佳奈 笹原
美代子 原
顕夫 田村
玲子 犬島
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Fujifilm Corp
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Fujifilm Corp
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B21/00—Microscopes
    • G02B21/34—Microscope slides, e.g. mounting specimens on microscope slides

Definitions

  • the present invention relates to an encapsulation method using a cover film.
  • a cover film prepared by applying an adhesive on a transparent support in advance is adhered by superimposing it on a slide glass on which a few drops of an organic solvent capable of swelling or dissolving the adhesive are dropped and a subject is placed.
  • encapsulation There is known a method of preparing a specimen for microscopic observation by allowing the sample to be encapsulated (hereinafter referred to as encapsulation).
  • Patent Document 1 describes transparency, a refractive index similar to that of glass slides, rapid interaction with an activating solvent, compatibility with coloring chemicals used in specimens, and long-term stability under high temperature and high humidity conditions.
  • a cover film showing the property is described, and limonene and the like are described as the encapsulating solvent in addition to xylene.
  • Toluene, ethyl acetate, methyl acetate, acetone, and methyl ethyl ketone are described as the encapsulating solvent in addition to xylene, but all solvents other than xylene are difficult to handle due to their low boiling points and lack versatility.
  • xylene In encapsulation using a cover film, xylene is generally widely used as an encapsulation solvent to dissolve the adhesive, but xylene is listed as a substance subject to the Women's Labor Standards Regulations, and it is preferable not to use it. Pinene, limonene, or alcan-based solvents are often used as alternatives to xylene, but there are cases where they cannot be sealed due to the low solubility of the cover film in the adhesive, and even if they can be sealed once, they adhere to each other. There was a problem that the property was poor and peeling occurred over time.
  • An object of the present invention is to provide an encapsulation method using a cover film having high safety and high encapsulation.
  • the encapsulating solvent contains an ester compound, and the boiling point of the ester compound is 80 to 170 ° C. , Encapsulation method.
  • the polymers contained in the adhesive polymer layer are ethyl acrylate, n-butyl acrylate, methyl acrylate, cyclohexyl acrylate, benzyl acrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methyl methacrylate, cyclohexyl methacrylate, and the like.
  • the polymers contained in the adhesive polymer layer are ethyl acrylate, n-butyl acrylate, methyl acrylate, cyclohexyl acrylate, benzyl acrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methyl methacrylate, cyclohexyl methacrylate, and the like.
  • the encapsulation method according to [3] which comprises a repeating unit derived from a monomer selected from the group consisting of benzyl methacrylate, acetoacetoxyalkyl methacrylate, styrene and dimethylacrylamide.
  • the encapsulation method according to any one of [1] to [8], wherein the adhesive polymer layer contains a silane coupling agent.
  • the above-mentioned silane coupling agent is at least one selected from the group consisting of ⁇ -glycidoxypropyltrimethoxysilane and N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, according to [9].
  • Encapsulation method is at least one selected from the group consisting of ⁇ -glycidoxypropyltrimethoxysilane and N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, according to [9].
  • the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
  • the amount of each component in the composition or layer is the sum of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition.
  • the refractive index means the refractive index for light having a wavelength of 550 nm, which is measured by using an Abbe refractometer (“NAR-2T” manufactured by Atago Co., Ltd.) unless otherwise specified.
  • the encapsulation method of the present invention includes a cover film provided with an adhesive polymer layer on a transparent support and an encapsulation solvent containing an ester compound having a boiling point in a specific range. It is characterized in that it is sealed using.
  • the present inventors have obtained xylene, limonene, etc. by using an ester compound having a boiling point in a specific range as the encapsulating solvent in a film with an adhesive polymer layer and a method of encapsulating using an encapsulating solvent. It was found that even if the regulated substance of the above is not used, it can be preferably sealed while ensuring high safety.
  • the base material and the cover film are formed by superimposing a cover film having a transparent support and an adhesive polymer layer on the surface of a base material (for example, slide glass) on which a subject is placed.
  • the method of adhering can be mentioned.
  • an encapsulating solvent is placed between the base material and the cover film, and the surface of the cover film on the adhesive polymer layer side is overlapped so as to face the base material.
  • a laminate used for applications such as specimens for microscopic observation is produced.
  • the method of arranging the encapsulation solvent between the base material and the cover film is not particularly limited, but a method of dropping the encapsulation solvent on the surface of the base material on which the subject to be encapsulated is placed is preferable. Further, the base material on which the subject is placed may be immersed in the encapsulating solvent, and after the immersion, the encapsulating solvent may be further dropped on the surface of the base material. In this case, the encapsulating solvent for immersing the base material and the encapsulating solvent dropped on the base material after immersion may be the same or different.
  • the encapsulation method may be automated encapsulation performed using a known automatic encapsulation device.
  • the encapsulating solvent refers to a solvent that can be mixed or dissolved with a polymer (hereinafter, also referred to as “adhesive polymer”) contained in the adhesive polymer layer of the cover film.
  • adhesive polymer a polymer contained in the adhesive polymer layer of the cover film.
  • the encapsulation method of the present invention is characterized in that the encapsulation solvent contains an ester compound having a boiling point in the range of 80 to 170 ° C. (hereinafter, also referred to as “specific ester compound”).
  • the specific ester compound is not particularly limited as long as it is within the provisions of the present invention, and is, for example, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, 3-methylbutyl acetate, ethyl propionate, ethyl butyrate, ethyl isobutyrate and the like.
  • Monocarboxylic acid ester of the volatility of the solvent is reduced, the odor when carrying out the encapsulation method can be further suppressed, and the quick-drying property is more excellent, that is, the solvent dries faster after encapsulation so that observation can be performed.
  • an ester compound having a boiling point in the range of 120 to 150 ° C. is more preferable, from the viewpoint of shortening the time until the temperature becomes equal to.
  • an ester compound having a boiling point in the range of 120 to 150 ° C. is more preferable, from the viewpoint of shortening the time until the temperature becomes equal to.
  • 3-methylbutyl acetate is particularly preferable from the viewpoint of encapsulation.
  • the specific ester compound may be used alone or in combination of two or more.
  • the encapsulating solvent may contain a solvent other than the specific ester compound.
  • the content of the specific ester compound in the encapsulating solvent is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 80% by mass or more, based on the total mass of the encapsulating solvent.
  • the upper limit is not particularly limited and may be 100% by mass with respect to the total mass of the encapsulating solvent. It is particularly preferable to use only the specific ester compound as the encapsulating solvent.
  • the transparent support of the cover film is not particularly limited, and all known transparent supports can be used.
  • “transparent” means that the transmittance of visible light (wavelength: 380 to 780 nm) is 60% or more.
  • the transmittance is the ratio of transmitted light to incident light of the support.
  • Examples of the material constituting the transparent support include cellulosic polymers such as triacetate cellulose (TAC) and diacetate cellulose, polyethylene terephthalate (PET), polycarbonate (PC) and polystyrene, and cellulosic polymers or polyethylene terephthalate ( PET) is preferable, and triacetate cellulose (TAC) is more preferable.
  • the thickness of the transparent support is preferably 50 to 250 ⁇ m, more preferably 50 to 150 ⁇ m, still more preferably 100 to 150 ⁇ m.
  • the refractive index of the transparent support is not particularly limited, but may be, for example, 1.440 to 1.600, and from the viewpoint of microscopic examination, the slide glass (refractive index 1.52 to 1.56) may be used. It is preferably close to 1.460 to 1.560.
  • the surface of the transparent support may be provided with an undercoat layer well known in the photographic photosensitive materials industry. The transparent support may be subjected to surface treatment such as ultraviolet irradiation, corona discharge or glow discharge.
  • the adhesive polymer layer (hereinafter, also simply referred to as “polymer layer”) contained in the cover film contains a polymer.
  • polymer layer contains a polymer.
  • the polymer constituting the polymer layer is a polymer that dissolves in the encapsulation solvent specified in the present application. By dissolving the polymer in the encapsulating solvent specified in the present application, the adhesiveness of the cover film to a substrate such as glass is improved. Further, it is preferable that the polymer constituting the polymer layer is swollen with the organic solvent used in the automatic encapsulation device.
  • an acrylic resin is preferable because it has excellent solubility in the encapsulating solvent specified in the present application.
  • the acrylic resin means a polymer having repeating units derived from an acrylate monomer and / or a methacrylate monomer.
  • the acrylic resin is not particularly limited as long as it has a repeating unit derived from an acrylate monomer and / or a methacrylate monomer, and is a homopolymer of one kind of monomer selected from the group consisting of an acrylate monomer and a methacrylate monomer. It may be a copolymer of two or more kinds of monomers selected from the group consisting of an acrylate monomer and a methacrylate monomer.
  • the acrylic resin has a common weight of at least one monomer selected from the group consisting of an acrylate monomer and a methacrylate monomer and at least one monomer other than the acrylate monomer and the methacrylate monomer (for example, an acrylamide monomer, a vinyl monomer, etc.). It may be a coalescence.
  • the content of the repeating unit derived from the acrylate monomer and / or the methacrylate monomer is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more, based on all the repeating units of the acrylic resin. Is more preferable.
  • the upper limit of the content of the repeating unit derived from the acrylate monomer and / or the methacrylate monomer is not particularly limited, and may be 100% by mass with respect to all the repeating units of the acrylic resin. It is particularly preferable that the acrylic resin has only repeating units derived from the acrylate monomer and / or the methacrylate monomer.
  • the acrylic resin can be prepared by a known method, for example, by polymerizing at least one monomer selected from the group consisting of an acrylate monomer and a methacrylate monomer.
  • Examples of the acrylate monomer and methacrylate monomer include alkyl acrylate and alkyl methacrylate.
  • Alkyl groups in alkyl acrylates and alkyl methacrylates may further have substituents.
  • Examples of the substituent include an aryl group, and a phenyl group is preferable.
  • the number of carbon atoms of the alkyl group which may have a substituent in the alkyl acrylate and the alkyl methacrylate is preferably 1 to 15, more preferably 1 to 8, further preferably 1 to 5, and particularly preferably 1 to 3.
  • alkyl acrylate examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, lauryl acrylate, benzyl acrylate, and , Acetacetoxyalkyl acrylates and the like.
  • alkyl methacrylate examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, lauryl methacrylate, and , Acetoxyalkyl methacrylate.
  • a polymer containing a repeating unit derived from at least one monomer selected from the group consisting of alkyl acrylate, alkyl methacrylate, styrene and acrylamide is particularly preferable in the encapsulation method specified in the present application. Is expressed.
  • the above-mentioned alkyl acrylates and alkyl methacrylates have the same meanings as those already described.
  • the above monomers include ethyl acrylate, n-butyl acrylate, methyl acrylate, cyclohexyl acrylate, benzyl acrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, methyl methacrylate, cyclohexyl methacrylate, and benzyl.
  • examples thereof include methacrylate, styrene, lauryl methacrylate, lauryl acrylate, acetoacetoxyalkyl methacrylate, acetoacetoxyalkyl acrylate, dimethylacrylamide and isopropylacrylamide.
  • a polymer containing a repeating unit derived from at least one monomer selected from the group consisting of dimethylacrylamide and dimethylacrylamide is preferable, and a polymer consisting of these repeating units is more preferable.
  • a polymer containing a repeating unit derived from at least one monomer selected from the group consisting of ethyl acrylate, methyl methacrylate, benzyl acrylate, ethyl methacrylate, n-butyl methacrylate, and cyclohexyl methacrylate is more preferable, and these repeating units are more preferable.
  • Polymers consisting of are particularly preferred.
  • the refractive index of the polymer layer is preferably 1.45 to 1.56, which is close to that of glass (refractive index 1.52 to 1.56), and 1.46 to 1. .56 is more preferable, and 1.47 to 1.56 is even more preferable.
  • the polymer constituting the polymer layer contains a repeating unit derived from at least one monomer selected from the group consisting of alkyl acrylates, alkyl methacrylates and styrenes. Is preferable.
  • the number of carbon atoms of the alkyl group in the alkyl acrylate and the alkyl methacrylate is preferably 1 to 5, and more preferably 1 to 3.
  • an acrylic resin composed of a combination of the repeating unit derived from the alkyl acrylate and the repeating unit derived from the alkyl methacrylate is preferable in that chips at the time of cutting can be further suppressed.
  • the content of the repeating unit derived from the alkyl acrylate and the content of the repeating unit derived from the alkyl methacrylate in such an acrylic resin are preferably 20 to 80% by mass with respect to all the repeating units of the acrylic resin. , 30-70% by mass is more preferable.
  • the total number of repeating units derived from alkyl acrylates and alkyl methacrylates having 1 to 5 carbon atoms in the alkyl group is 60 with respect to all the repeating units of the acrylic resin in that chips at the time of cutting can be further suppressed.
  • Acrylic resin having an amount of about 100% by mass is more preferable, and acrylic resin having an amount of 75 to 100% by mass is further preferable.
  • the adhesive polymer has a higher encapsulation property when the solubility in the encapsulation solvent specified in the present application is higher.
  • Hansen solubility parameter Hansen SP value
  • the adhesive polymer preferably has a hydrogen bond term dH of 1.0 to 9.0, more preferably 2.0 to 8.0, and 2.5 to 7.0 in the Hansen SP value. Is more preferable.
  • the polarity term dP in the Hansen SP value is preferably 1.0 to 9.0, more preferably 2.0 to 8.0, and even more preferably 2.5 to 7.0. .. When it is within the above range, it is particularly preferable that the solvent tends to be close to the encapsulating solvent specified in the present application, and high solubility is exhibited.
  • the weight average molecular weight (Mw) of the polymer is preferably 10,000 to 150,000, more preferably 30,000 to 100,000.
  • the weight average molecular weight (Mw) is a column of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL and / or TSKgel Super HZM-N (all trade names manufactured by Toso Co., Ltd.) unless otherwise specified. It is a molecular weight converted by using a gel permeation chromatography (GPC) analyzer used, using THF (tetrahexyl) as a solvent, detecting with a differential refractometer, and using polystyrene as a standard substance.
  • GPC gel permeation chromatography
  • the polymer constituting the polymer layer may be used alone, or may be used by blending two or more kinds of polymers.
  • each polymer is prevented from becoming turbid after the solvent evaporates. It is preferable to adjust the usage ratio as appropriate.
  • the polymer layer may contain components other than the above polymer. Examples of the components other than the polymer that the polymer layer may contain include a silane coupling agent described later, a thickener such as inorganic particles, a solvent, and a plasticizer.
  • the content of the polymer in the polymer layer is not particularly limited, but is preferably 85% by mass or more, more preferably 90% by mass or more, based on the total mass of the polymer layer.
  • the upper limit may be 100% by mass or less, preferably 99.99% by mass or less, and more preferably 99.95% by mass or less.
  • the amount of the polymer with respect to the surface area of the transparent support is preferably about 1 to 50 g / m 2 , more preferably 7 to 25 g / m 2 . If it is too small, the adhesiveness to the slide glass may decrease, and if it is too thick, the maneuverability of the cover film may decrease. Further, the thinner the polymer layer, the lower the adhesiveness and the smaller the stress applied at the time of cutting, so that blocking can be suppressed and the generation of chips at the time of cutting can be suppressed.
  • the thickness of the polymer layer is not particularly limited, but 1 ⁇ m or more is preferable, and 10 ⁇ m or more is more preferable, because the adhesiveness to the slide glass is more excellent.
  • the upper limit of the thickness of the polymer layer is preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less, in that the cover film is more easily handled. From the viewpoint of suppressing blocking and suppressing the generation of chips during cutting, 20 ⁇ m or less is preferable, and 15 ⁇ m or less is more preferable.
  • the method of providing the polymer layer on the transparent support is not particularly limited, and examples thereof include coating by a coater or a spray, casting, and transfer. Above all, it is preferable to apply a coating liquid obtained by dissolving a polymer in a solvent on a transparent support and then dry the coating film to form a polymer layer.
  • a solvent that can dissolve the polymer and has a wettability so as not to generate "repellency" on the substrate is preferably used.
  • solvents include toluene, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone and xylene. If a material capable of dissolving the surface of the transparent support or a material capable of eluting low molecular weight components such as a plasticizer contained in the transparent support is used as the solvent used for the coating liquid, the polymer penetrates into the surface layer of the transparent support.
  • the coating liquid used for forming the polymer layer preferably contains a solvent selected from the group consisting of ethyl acetate and butyl acetate, and more preferably contains ethyl acetate.
  • the content of the solvent selected from the group consisting of ethyl acetate and butyl acetate in the coating liquid is not particularly limited, but all of the solvents contained in the coating liquid can further suppress the generation of chips when the cover film is cut.
  • the mass 40% by mass or more is preferable, 60% by mass or more is more preferable, and 70% by mass or more is further preferable.
  • the upper limit is not particularly limited and may be 100% by mass or less, but 90% by mass or less is preferable in that deformation of the base material can be further suppressed.
  • the drying treatment performed in the drying step includes a method of leaving the coating film at room temperature (23 ° C.) for a predetermined time (for example, natural drying), blast drying by blowing gas onto the coating film, and heating means such as an oven. Heat drying for heating the coating film using the above, and a combination thereof can be mentioned.
  • the drying step it is preferable to perform at least one of blast drying and heat drying, and it is more preferable to perform blast drying and heat drying in combination.
  • the temperature of the gas used for blast drying is not particularly limited, but is preferably 50 to 160 ° C, more preferably 80 to 140 ° C.
  • the airflow velocity (wind velocity) in the blast drying is not particularly limited, but is preferably 3 to 15 m / s, more preferably 5 to 10 m / s.
  • the treatment time for blast drying is preferably 0.5 to 5 minutes. Examples of the gas used for blast drying include air and nitrogen. As described above, the coating film containing the polymer formed on the transparent support is blown and dried, and the above gas is used according to the type of the polymer constituting the polymer layer, the target average height Rc, and the like.
  • the average height Rc of the surface of the polymer layer of the cover film can be adjusted by appropriately changing conditions such as temperature, air flow velocity, and drying time. For example, if the temperature of the gas is too low, it may be difficult to form irregularities on the surface of the polymer layer, and if the temperature of the gas is too high, it may be difficult to maintain the irregular shape formed on the surface. Further, the higher the velocity of the air flow, the larger the unevenness of the surface of the polymer layer, that is, the average height Rc tends to be.
  • the temperature for heating and drying is not particularly limited, but is preferably 50 to 160 ° C.
  • the heating time is preferably 0.5 to 5 minutes.
  • the polymer layer may contain a silane coupling agent.
  • the silane coupling agent has two or more different reactive groups in the molecule, at least one of the reactive groups is a reactive group that chemically bonds with an inorganic substance, and at least one of the other is an organic material. It is an organic silicon monomer that is a reactive group that chemically bonds.
  • the polymer layer preferably contains a silane coupling agent. This is because even if the cover film is adhered to the cover glass and the sample is enclosed and then stored for a long period of time, the cover film is less likely to peel off from the glass, which is particularly remarkable in the encapsulation method specified in the present application. Even if the cover film is stored in a roll or laminated, it also has an effect that blocking is less likely to occur between the polymer layer and the back surface of the support.
  • Preferred silane coupling agents include silane coupling agents represented by the following general formulas. YR-Si (CH 3 ) 3-n X n (In the formula, Y represents a vinyl group, a methacryl group, an epoxy group, an amino group, a mercapto group or a chloro group; R is a single bond, a methylene group, a polymethylene group or at least one methylene group placed in O, S or NH. Represents an alternative polymethylene group; X represents a chloro group, a methoxy group, an ethoxy group, a methoxyethoxy group, an acetoxy group, a methylvinyloxy group, or an amino group; n is 2 or 3. Note that a plurality of Xs are used. It may be the same or different.)
  • silane coupling agent examples include vinyltrichlorosilane, vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ - (methacryloxypropyl) trimethoxysilane, and ⁇ - (3,4).
  • the type of silane coupling agent used for the polymer layer is selected according to the organic material to be adhered to the glass, that is, the type of the polymer constituting the polymer layer. ..
  • the method for incorporating the silane coupling agent in the polymer layer is not particularly limited, but for example, the silane coupling agent is added in advance to the coating liquid for forming the polymer layer, and the polymer and the silane coupling agent are contained on the transparent support.
  • the first method of applying the coating liquid and drying the coating liquid is to apply a coating liquid obtained by dissolving a silane coupling agent in a solvent on the surface of the coating film or the polymer layer containing the polymer formed on the transparent support.
  • a second method of coating and drying the coating film, and a coating liquid containing a polymer and a coating liquid obtained by dissolving a silane coupling agent in a solvent are simultaneously applied (multilayer coating) on a transparent support.
  • a third method of drying the coating film can be mentioned.
  • the above-mentioned second method and third method are preferable in that the silane coupling agent can be effectively utilized in a small amount.
  • the first layer composed of the polymer and the second layer composed of the silane coupling agent are laminated. It has a layered structure consisting of That is, in the cover film formed by the above-mentioned second method and the third method, the transparent support, the first layer composed of the polymer and the second layer composed of the silane coupling agent are laminated in this order. It has a layered structure.
  • the polymer layer composed of the first layer and the second layer is formed by performing the above-mentioned blast drying in the step of drying the coating film. It is possible to form an uneven shape having a desired average height Rc on the surface of the above.
  • the solvent of the coating liquid obtained by dissolving the silane coupling agent in the solvent used in the second method and the third method is not particularly limited as long as the silane coupling agent can be dissolved, and for example, the above.
  • Examples of the solvent that can dissolve the polymer of the above are listed. Of these, ethyl acetate is preferable because it is superior in improving adhesion.
  • the content of the silane coupling agent contained in the polymer layer is preferably 0.1 mg / m 2 or more, preferably 5 to 25 mg / m 2 with respect to the surface area of the cover film. More preferred.
  • the total film thickness of the polymer layer and the transparent support in the cover film is not particularly limited, but is preferably 250 ⁇ m or less, more preferably 200 ⁇ m or less, and further preferably 150 ⁇ m or less from the viewpoint of operability and microscopic examination during microscopic observation. preferable.
  • the lower limit is preferably 50 ⁇ m or more from the viewpoint of handleability such as breakage resistance and encapsulation.
  • the polymer layer preferably has an average height Rc of 1.0 ⁇ m or more on its surface.
  • average height Rc hereinafter, also simply referred to as “average height Rc”
  • the unevenness of the surface of the polymer layer becomes large, and the surface of the polymer layer and others Since the contact area with the member is small, blocking is less likely to occur in the polymer layer even when the cover film is rolled or laminated and stored for a long period of time.
  • the "surface" of the polymer layer is intended to be the surface of the polymer layer opposite to the surface facing the transparent support.
  • the average height Rc of the surface of the polymer layer means the average height of the roughness curve elements specified in JIS B0601: 2013.
  • the average height Rc of the surface of the polymer layer is preferably 1.5 ⁇ m or more, and more preferably 2.0 ⁇ m or more, in that blocking can be further suppressed.
  • the upper limit of the average height Rc is not particularly limited, but if the unevenness is large, a thicker polymer layer is required and the film thickness of the entire cover film becomes thicker. It is preferably 10.0 ⁇ m or less, more preferably 3.5 ⁇ m or less.
  • the average height Rc of the surface of the polymer layer can be measured by image analysis using a laser microscope. For example, using "VK-9710" manufactured by KEYENCE, the average height of the unevenness in the sections was measured at 5 arbitrarily selected sections (length of 1056 ⁇ m) on the surface of the polymer layer. The average height Rc of the surface of the polymer layer is calculated by averaging the average heights of the sections.
  • the method for adjusting the average height Rc on the surface of the polymer layer is not particularly limited as long as it is a method for forming irregularities on the surface of the polymer layer.
  • a method for forming irregularities on the surface of the polymer layer for example, in the step of applying a coating liquid obtained by dissolving a polymer in the above solvent on a transparent support and then drying the coating film, a gas is blown to the coating film for air drying. And a method of pressing a release film having an uneven surface against the coating film or the polymer layer to transfer the shape of the unevenness to the coating film or the polymer layer.
  • the viscosity of the coating liquid is adjusted by the polymer content in the coating liquid, the weight average molecular weight (Mw) of the polymer contained in the coating liquid, the glass transition temperature (Tg) of the polymer layer, the addition of a thickener, and the like. can.
  • the glass transition temperature Tg of the polymer layer is preferably 80 ° C. or lower, more preferably 70 ° C. or lower, from the viewpoint of improving the brittleness of the film and further suppressing the generation of chips when the cover film is cut. 60 ° C. or lower is more preferable.
  • the lower limit of the glass transition temperature Tg of the polymer layer is not particularly limited, but 20 ° C. or higher is preferable in that the viscoelasticity of the polymer layer is lowered, it becomes difficult to adhere to other members, and the blocking resistance is further improved. 45 ° C. or higher is more preferable.
  • the glass transition temperature Tg of the polymer layer is measured by a differential scanning calorimetry (DSC) after collecting a sample of the polymer layer by a method such as peeling or scraping the polymer layer from the cover film. By doing so, it can be obtained. Further, the glass transition temperature Tg of the polymer layer can be adjusted by the type and content ratio of the polymer constituting the polymer layer.
  • DSC differential scanning calorimetry
  • the polymer layer may contain a thickener.
  • the type of thickener contained in the polymer layer is not particularly limited, but is limited to polysaccharides, celluloses, acrylics, polyvinyl alcohol, polymer compounds such as diols and terpenes, inorganic particles such as silica particles and titania particles, and PMMA. Examples thereof include organic particles made of a polymer such as cellulose acetate (more preferably cellulose acetate butyrate or cellulose acetate phthalate) or silica particles.
  • the surface of the inorganic particles is preferably hydrophobized in that the exudation (migration) of the hydrophilic material from the member in contact with the polymer layer can be suppressed.
  • the sizes of the inorganic particles and the organic particles are not particularly limited, but if they are too large, scattering is likely to occur and the microscopic property may be deteriorated. Therefore, the average secondary particle diameter of the inorganic particles (the average particle diameter of the aggregates of the inorganic particles). ) Is preferably 1 ⁇ m or less. The lower limit is not particularly limited and may be 1 nm or more.
  • the average secondary particle diameter of the inorganic particles and the organic particles can be measured by using a dynamic light scattering method (nanoSAQLA manufactured by Otsuka Electronics Co., Ltd.). Further, it is preferable that the refractive index of the inorganic particles and the organic particles is close to the refractive index of the polymer layer in that scattering can be prevented. More specifically, the refractive index of the inorganic particles and the organic particles is preferably 1.40 to 1.60.
  • the polymer layer may contain a plasticizer.
  • a plasticizer such as triphenyl phosphate, bisphenol A bis- (diphenyl phosphate), trimethyl phosphate, triethyl phosphate and diphenyl-2-methacryloyl ethyl phosphate; Plastics selected from the group consisting of adipic acid esters such as dioctyl adipate, dibutyl adipate and diisobutyl adipate; sebacic acid esters such as dioctyl sebacate; tris (2-ethylhexyl) trimellitate; dibutyl maleate; and glycerin triacetate. Agents are preferred.
  • the content of each is not particularly limited, but from the viewpoint of more exerting the effect of each additive, it is 0 with respect to the total mass of the polymer. 5.5% by mass or more is preferable, 1% by mass or more is more preferable, and 3% by mass or more is further preferable. Above all, it is particularly preferable that the content of the thickener selected from the group consisting of the above-mentioned inorganic particles and organic particles contained in the polymer layer is in the above-mentioned range in that chips at the time of cutting can be further suppressed.
  • the upper limit of the content of the additive is not particularly limited, but from the viewpoint of the adhesiveness of the polymer layer, it is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less with respect to the total mass of the polymer. More preferred.
  • the back surface of the support ( A backing layer may be provided on the surface opposite to the surface on which the polymer layer is provided).
  • the constituent material of the backing layer include synthetic polymers having a high glass transition temperature such as polystyrene and polymethylmethacrylate, and gelatin.
  • the above-mentioned encapsulation method can be particularly preferably applied to the preparation of a specimen in a microscope having an automatic encapsulation device.
  • the above-mentioned encapsulation method is not limited to the application to the preparation of the above-mentioned specimen, and can be applied to, for example, encapsulation of a thin film on a substrate, protection of a lower layer by laminating, and the like.
  • the base material to which the cover film is attached may be glass or a film-shaped material (resin or the like).
  • [Making cover film A] (Polymer synthesis) 60 parts by mass of ethyl acrylate, 150 parts by mass of methyl methacrylate, 90 parts by mass of cyclohexyl methacrylate, 98 parts by mass of toluene, ethyl acetate with respect to a mixture of 38 parts by mass of toluene and 25 parts by mass of ethyl acetate under a nitrogen atmosphere at 80 ° C.
  • a mixed solution of 66 parts by mass and 1.8 parts by mass of azoisobutyronitrile was added over 2 hours. Then, the obtained mixed solution was reacted for 2 hours while maintaining 80 ° C.
  • a polymer layer coating solution 1 and a silane coupling agent coating solution 1 are applied to a substrate (transparent support, refractive index: 1.481) made of transparent triacetate cellulose (TAC) having a thickness of 118 ⁇ m by an extrusion layer coating method. It was applied to form a coating.
  • the coating amount of the polymer layer coating liquid 1 is an amount such that the film thickness after drying is 19 ⁇ m, and the coating amount of the silane coupling agent coating liquid 1 is the coating concentration of the silane coupling agent with respect to the surface area of the transparent support.
  • the coating amount of the silane coupling agent coating liquid 1 is the coating concentration of the silane coupling agent with respect to the surface area of the transparent support.
  • the formed coating film is blown and dried by applying warm air at 100 ° C.
  • a cover film A composed of a transparent support and a polymer layer having a silane coupling agent layer on the surface side.
  • the total film thickness of the transparent support and the polymer layer in the cover film A was 137 ⁇ m.
  • the cover film B was produced.
  • the total film thickness of the transparent support and the polymer layer in the cover film B was 137 ⁇ m.
  • [Making cover film C] In the preparation of the polymer solution, 60 parts by mass of ethyl acrylate, 150 parts by mass of methyl methacrylate and 90 parts by mass of n-butyl methacrylate were used instead of 60 parts by mass of ethyl acrylate, 150 parts by mass of methyl methacrylate and 90 parts by mass of cyclohexyl methacrylate.
  • a polymer solution 2 containing a polymer was prepared in the same manner as the cover film A except for the above.
  • the weight average molecular weight Mw of the polymer contained in the polymer solution 2 was 70,000.
  • a cover film C was produced in the same manner as the cover film A, except that the obtained polymer layer coating liquid 2 was used instead of the polymer layer coating liquid 1.
  • the total film thickness of the transparent support and the polymer layer in the cover film C was 137 ⁇ m.
  • silica particles (“Aerosil NX90S”, manufactured by EVONIK) are ultrasonically dispersed in ethyl acetate to adjust the concentration, and the content of silica particles having an average secondary particle size of 0.2 ⁇ m is 5% by mass.
  • the silica-containing liquid 1 contained in the above was prepared.
  • 118 parts by mass of toluene, 275 parts by mass of ethyl acetate, and 300 parts by mass of silica-containing liquid 1 are added to 608 parts by mass of the polymer solution 2 and mixed to prepare the polymer layer coating liquid 3. did.
  • a cover film D was produced in the same manner as the cover film A, except that the obtained polymer layer coating liquid 3 was used in place of the polymer layer coating liquid 1.
  • the total film thickness of the transparent support and the polymer layer in the cover film D was 137 ⁇ m.
  • [Making cover film E] Similar to cover film A, the polymer was contained in the preparation of the polymer solution, except that 300 parts by mass of ethyl acrylate was used instead of 60 parts by mass of ethyl acrylate, 150 parts by mass of methyl methacrylate and 90 parts by mass of cyclohexyl methacrylate.
  • the polymer solution 4 to be prepared was prepared.
  • the weight average molecular weight Mw of the polymer contained in the polymer solution 4 was 70,000.
  • the polymer layer coating liquid 4 was prepared by using the polymer solution 4 instead of the polymer solution 1, and the obtained polymer layer coating liquid 4 was used instead of the polymer layer coating liquid 1.
  • the cover film E was produced.
  • the total film thickness of the transparent support and the polymer layer in the cover film E was 137 ⁇ m.
  • Table 1 shows the composition and physical properties of the produced cover films A to E.
  • the "Monomer ratio (%)” column of "Polymer layer” the type of monomer used for synthesizing the polymer constituting the polymer layer and the ratio of the repeating unit derived from each monomer to the total repeating unit of the polymer. (Mass%) is shown.
  • the “Ethyl acetate ratio (%) (in all solvents)” column shows the ratio (% by mass) of ethyl acetate to all the solvents contained in each polymer layer coating liquid.
  • the “Blower drying condition” column shows the conditions of the blast drying treatment among the drying steps for drying the coating film of the polymer layer coating liquid, which were performed when each cover film was produced.
  • the “total film thickness ( ⁇ m)” column shows the total film thickness (unit: ⁇ m) of the transparent support and the polymer layer of the produced cover film.
  • the “silane coupling agent layer” column indicates the silane coupling agent used to form the silane coupling agent layer in the production of the cover film, and describes “none” when the silane coupling agent layer is not formed. do.
  • the “Hansen solubility parameter” column indicates the silane coupling agent used to form the silane coupling agent layer in the production of the polymer layer cover film, and is described as “none” if the silane coupling agent layer is not formed. do.
  • Example 1 (Encapsulation work) The slide glass dipped in 3-methylbutyl acetate, which is a pre-soaking solvent, is lifted from the dipping layer, 0.07 ml of 3-methylbutyl acetate is added dropwise to the slide glass, and the cover film A is semi-reciprocated at 0.05 MPa from above. And pasted together.
  • evaluation The following evaluations were performed during and after the encapsulation work.
  • Drying time The time from the completion of the encapsulation work until the adhesive dries and the film does not move (drying time) was measured, and the quick-drying property was evaluated based on the following criteria. 1: Drying time is within 3 minutes. 2: Drying time is within 5 minutes. 3: Drying time is within 10 minutes. 4: Drying time is within 15 minutes. 5: Drying time is over 15 minutes.
  • Example 2 Comparative Examples 1 to 2
  • the encapsulation test and each evaluation were carried out in the same manner as in Example 1 except that the pre-immersion solvent, the encapsulation solvent, and / or the cover film were changed as shown in Table 2.
  • a mixed solvent of 3-methylbutyl acetate and acetone 3-methylbutyl acetate: acetone mass ratio: 7: 3) was used as the encapsulating solvent.
  • the "pre-soaking solvent” column and the “solvent type” column of "encapsulating solvent” indicate the type of solvent used in each Example and each comparative example, and the “boiling point (° C.)” of “encapsulating solvent” is shown.
  • ) Column indicates the boiling point (unit: ° C.) of the ester compound contained as the encapsulating solvent.
  • the "Type” column of “Cover film” indicates the cover film used in each Example and each comparative example, and the “Hansen solubility parameter” column of “Cover film” indicates the polymer constituting the polymer layer of each cover film. The Hansen solubility parameter (Hansen SP value) is shown.
  • the "silane coupling agent” column indicates the silane coupling agent used for forming the silane coupling agent layer in each Example and each comparative example, and if the cover film used does not have the silane coupling agent layer. Describe as "None”.
  • Example 1 to 12 the coating concentration when the same amount of toluene, the same amount of ethyl acetate, and the silane coupling agent coating liquid was applied instead of the addition of toluene and ethyl acetate to each polymer solution.
  • a polymer layer coating liquid containing a silane coupling agent was prepared by adding and mixing a mixed liquid of a silane coupling agent in an amount having the same coating concentration as the above, and in (preparation of a cover film), the polymer layer coating liquid was prepared.
  • a cover film was produced in the same manner as in Examples 1 to 12 except that the above-mentioned single layer coating of the silane coupling agent-containing polymer layer coating liquid was performed.
  • the encapsulation test was carried out, and it was confirmed that the performance was similar to that of Examples 1 to 12.

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Abstract

La présente invention aborde le problème de la fourniture d'un procédé d'encapsulation qui utilise un film de recouvrement qui présente une sécurité élevée et une performance d'encapsulation élevée.　Un procédé d'encapsulation selon la présente invention est mis en œuvre à l'aide d'un solvant d'encapsulation et d'un film de recouvrement qui est obtenu en fournissant une couche de polymère adhésif sur un support transparent ; le solvant d'encapsulation contient un composé ester ; et le composé ester a un point d'ébullition de 80 °C à 170 °C.
PCT/JP2021/025134 2020-07-14 2021-07-02 Procédé d'encapsulation Ceased WO2022014374A1 (fr)

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JP2020120421 2020-07-14

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024070525A1 (fr) * 2022-09-30 2024-04-04 富士フイルム株式会社 Film de couverture
CN119193075A (zh) * 2024-10-17 2024-12-27 北京东杰华医医疗器械有限公司 一种快速固化的标本封胶及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61254916A (ja) * 1985-05-07 1986-11-12 Mitsubishi Rayon Co Ltd 顕微鏡用カバ−グラス
JPS6238408A (ja) * 1985-08-13 1987-02-19 Fuji Photo Film Co Ltd 顕微鏡用カバ−フイルム
JPH1054942A (ja) * 1996-08-09 1998-02-24 Yasuhara Chem Kk プレパラート用封入剤
JPH11101943A (ja) * 1997-09-29 1999-04-13 Fuji Photo Film Co Ltd 顕微鏡用カバーフイルム
JP2004506228A (ja) * 2000-08-07 2004-02-26 スリーエム　イノベイティブ　プロパティズ　カンパニー 顕微鏡用カバースリップ材
JP2009514025A (ja) * 2005-10-26 2009-04-02 リー エイチ． アングロス， 顕微鏡カバースリップおよびその使用
US20180194913A1 (en) * 2015-06-23 2018-07-12 Island Polymer Industries Gmbh Highly transparent coated cellulose triacetate film and dissolver medium

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61254916A (ja) * 1985-05-07 1986-11-12 Mitsubishi Rayon Co Ltd 顕微鏡用カバ−グラス
JPS6238408A (ja) * 1985-08-13 1987-02-19 Fuji Photo Film Co Ltd 顕微鏡用カバ−フイルム
JPH1054942A (ja) * 1996-08-09 1998-02-24 Yasuhara Chem Kk プレパラート用封入剤
JPH11101943A (ja) * 1997-09-29 1999-04-13 Fuji Photo Film Co Ltd 顕微鏡用カバーフイルム
JP2004506228A (ja) * 2000-08-07 2004-02-26 スリーエム　イノベイティブ　プロパティズ　カンパニー 顕微鏡用カバースリップ材
JP2009514025A (ja) * 2005-10-26 2009-04-02 リー エイチ． アングロス， 顕微鏡カバースリップおよびその使用
US20180194913A1 (en) * 2015-06-23 2018-07-12 Island Polymer Industries Gmbh Highly transparent coated cellulose triacetate film and dissolver medium

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024070525A1 (fr) * 2022-09-30 2024-04-04 富士フイルム株式会社 Film de couverture
CN119193075A (zh) * 2024-10-17 2024-12-27 北京东杰华医医疗器械有限公司 一种快速固化的标本封胶及其制备方法

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