WO2021112132A1 - Film fonctionnel, composition durcissable de type film, procédé de production de film fonctionnel et procédé de transport d'article - Google Patents

Film fonctionnel, composition durcissable de type film, procédé de production de film fonctionnel et procédé de transport d'article Download PDF

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Publication number
WO2021112132A1
WO2021112132A1 PCT/JP2020/044895 JP2020044895W WO2021112132A1 WO 2021112132 A1 WO2021112132 A1 WO 2021112132A1 JP 2020044895 W JP2020044895 W JP 2020044895W WO 2021112132 A1 WO2021112132 A1 WO 2021112132A1
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Prior art keywords
curable composition
functional film
film
pattern
meth
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PCT/JP2020/044895
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English (en)
Japanese (ja)
Inventor
茂 栗本
博司 大▲崎▼
昂平 平尾
達也 熊田
麗 佐竹
和彦 森
Original Assignee
昭和電工マテリアルズ株式会社
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Priority claimed from JP2020081981A external-priority patent/JP2021091855A/ja
Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Publication of WO2021112132A1 publication Critical patent/WO2021112132A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/14—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by a layer differing constitutionally or physically in different parts, e.g. denser near its faces
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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

Definitions

  • the present invention relates to a functional film, a film-like curable composition, and a method for producing a functional film.
  • the present invention also relates to a method for transporting an article using a functional film.
  • the present invention has been made in view of the above circumstances, and is a functional film capable of selectively adhering an article to a predetermined portion, a film-like curable composition capable of obtaining the functional film, and a functional film. It is an object of the present invention to provide a manufacturing method and a method for transporting an article using a functional film.
  • the present inventors have focused on using a functional film having adhesiveness as a means for transporting an article, and as a result of diligent studies on arranging a large number of parts in a predetermined position or range, a specific storage elastic modulus It was found that a film having a low-hardness portion made of a cured resin product having a resin and a high-hardness portion made of a cured resin product having a higher storage elastic modulus than the low-hardness portion can selectively attach an article to the low-hardness portion.
  • the present invention has been completed.
  • One aspect of the present invention is a functional film having portions having different hardness, and has a pattern of a first resin cured product having a storage elastic modulus of 0.01 MPa or more and a storage higher than that of the first resin cured product.
  • a functional film containing a second resin cured product pattern having an elastic modulus is provided.
  • the pattern of the first cured resin product may be a low-hardness portion where the adhesiveness is exhibited, and the pattern of the second cured resin product may be a high-hardness portion where the adhesiveness is suppressed. It is possible to selectively attach the article to the pattern of the first cured resin product. Further, according to the above-mentioned functional film, by setting the pattern shape of the first resin cured product according to the shape in which the articles are arranged, a large amount of articles (for example, electronic parts, etc.) can be placed in a predetermined position or range. Can be placed efficiently.
  • the above-mentioned functional film can secure rigidity by the pattern of the second cured resin product, it can be hard to be distorted while having adhesiveness and excellent in transportability.
  • the storage elastic modulus of the second cured resin product is preferably twice or more the storage elastic modulus of the first cured resin product. ..
  • the storage elastic modulus of the first cured resin product is preferably 0.01 to 1000 MPa.
  • the above functional film may be used for transporting goods.
  • Another aspect of the present invention is a film-like curable composition for forming a functional film having sites having different hardness, which comprises (i) a photoradical polymerization initiator and a thermosetting functional group. Contains a compound having a radically polymerizable functional group, or (ii) a photoradical polymerization initiator, a photocationic polymerization initiator, a compound having a radically polymerizable functional group, and a compound having a cationically polymerizable functional group. , A film-like curable composition is provided.
  • Another aspect of the present invention is a method for producing a functional film having portions having different hardness, which is a step of preparing a curable composition which is in the form of a film and has photocurability, and in the curable composition.
  • a method for producing a functional film comprising.
  • one region where exposure is repeated can be a high hardness region and the other region can be a low hardness region, and a functional film having these regions having different hardness can be obtained.
  • the obtained functional film can selectively attach the article to the low hardness portion.
  • Another aspect of the present invention is a method for producing a functional film having portions having different hardness, which comprises a base material and a pattern of a first cured resin product provided on the base material.
  • a method for producing a functional film which comprises a step of providing a second resin cured product having a hardness different from that of the first resin cured product between patterns of the resin cured product.
  • a functional film having a pattern of a first cured resin product and a second cured resin product provided between the patterns can be obtained as portions having different hardness. ..
  • the obtained functional film can selectively attach an article to a portion made of a cured resin product having a lower hardness.
  • Another aspect of the present invention is a method for producing a functional film having portions having different hardness, which is a step of preparing a curable composition which is in the form of a film and has thermosetting and photocuring properties, and curing.
  • a method for producing a functional film which comprises a step of subjecting a sex composition to heating and pattern exposure.
  • thermosetting and pattern a region exposed to thermosetting and pattern can be designated as a high hardness region, and a region not exposed by thermosetting can be designated as a low hardness region.
  • a functional film having parts having different hardnesses can be obtained. The obtained functional film can selectively attach the article to the low hardness portion.
  • Another aspect of the present invention is a method for producing a functional film having portions having different hardness, which is a pattern of the first curable composition by applying the curable composition on a substrate. And the step of forming a film-like curable composition containing the pattern of the second curable composition, the curing of the pattern of the first curable composition, and the curing of the pattern of the second curable composition.
  • a method for producing a functional film which comprises a step of performing the above.
  • a portion where the pattern of the first curable composition is cured and a portion where the pattern of the second curable composition is cured are defined as portions having different hardness.
  • a functional film can be obtained.
  • the obtained functional film can selectively attach the article to the portion having the lower hardness.
  • Another aspect of the present invention is a method of transporting an article on a base material onto another base material, in which a functional film according to the above aspect of the present invention is prepared and the article on the base material is used.
  • a step of pressing the functional film to attach an article to the first cured resin product in the functional film, and a step of transferring the article adhering to the first cured resin product onto another base material. Provide a method for transporting an article.
  • a large amount of articles for example, electronic parts
  • a functional film capable of selectively adhering an article to a predetermined portion a film-like curable composition capable of obtaining the functional film, a method for producing the functional film, and a functional film are used.
  • a method of transporting goods can be provided.
  • FIG. 1 is a schematic view showing an embodiment of a functional film according to the present invention.
  • FIG. 2 is a top view showing another embodiment of the functional film according to the present invention.
  • FIG. 3 is a schematic diagram for explaining an embodiment of a method for producing a functional film according to the present invention.
  • FIG. 4 is a schematic diagram for explaining another embodiment of the method for producing a functional film according to the present invention.
  • FIG. 5 is a schematic view for explaining another embodiment of the method for producing a functional film according to the present invention.
  • FIG. 6 is a schematic view for explaining an embodiment in which the functional film according to the present invention is applied to transporting articles.
  • (meth) acrylic acid means acrylic acid or methacrylic acid
  • (meth) acrylate means acrylate or the corresponding methacrylate
  • (meth) acryloyl means an acryloyl group or a methacryloyl group.
  • a or B may include either A or B, or both.
  • 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.
  • each component in the composition 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. Means quantity. Further, the exemplary materials may be used alone or in combination of two or more unless otherwise specified.
  • the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • the functional film of the present embodiment includes portions having different hardness.
  • film refers to a thin film or plate, and the thickness is not particularly limited. Films also include sheets, plates and films.
  • the functional film of the present embodiment can include a low hardness portion having a storage elastic modulus of 0.01 MPa or more and a high hardness portion having a storage elastic modulus higher than that of the low hardness portion as portions having different hardness. ..
  • the functional film of the present embodiment can selectively attach an article to a low hardness portion. Further, since the functional film of the present embodiment can secure rigidity by a high hardness portion, it can be hard to be distorted while having adhesiveness and can be excellent in transportability.
  • the storage elastic modulus means a measured value under the following measurement conditions using a nanoindenter (manufactured by BRKER, “TI 980 TriboIndenter”).
  • Measuring head Standard (1D) Transducer and Piezo Scanner Indenter: Berkovich (tip: diamond)
  • the storage elastic modulus of the low hardness portion is preferably 0.01 MPa or more and 10 GPa or less, more preferably 0.1 MPa or more and 1 GPa or less, from the viewpoint of improving the adhesiveness of the article and preventing damage to the article. It is more preferably 1 MPa or more and 100 MPa or less.
  • the storage elastic modulus of the high hardness portion is preferably more than 0.01 MPa and 100 GPa or less, more preferably 0.1 MPa or more and 20 GPa or less, and 1 MPa or more and 20 GPa or less. Is even more preferable.
  • the storage elastic modulus of the high hardness part is 1.5 times or more, 2 times or more, 5 times or more, 10 times or more, 50 times the storage elastic modulus of the low hardness part. It may be double or more, 100 times or more, or 1,000 times or more. From the viewpoint of flexibility and flexibility, the storage elastic modulus of the high hardness part is 10,000,000 times or less, 1,000,000 times or less, 100,000 times or less, or 10 times the storage elastic modulus of the low hardness part. It may be 000 times or less.
  • the low hardness part and the high hardness part may each have a pattern.
  • Patterns include stripes, dots (circles), honeycombs, lattices, checkered patterns (square geometric patterns), scale patterns (triangular geometric patterns), hemp leaves, cones (triangular pyramids, quadrangular pyramids, cones, etc.), etc. Can be mentioned.
  • the pattern may include one of these shapes alone or in combination of two or more.
  • the pattern in the functional film may have a different shape in the depth direction.
  • the functional film of the present embodiment can be used for transporting articles, and in that case, the pattern shape of the low hardness portion can be set according to the shape in which the articles are arranged. As a result, a large amount of articles (for example, electronic parts, etc.) can be efficiently arranged at a predetermined position or range.
  • FIG. 1 is a schematic view showing an embodiment of a functional film, (a) is a top view, and (b) is a cross-sectional view taken along the line II shown in (a).
  • the functional film 100 with a support base material shown in FIG. 1 includes a support base material 20 and a functional film 10 provided on the support base material 20.
  • the functional film 10 is composed of a low-hardness portion 1 having a striped pattern and a high-hardness portion 2.
  • FIG. 2 is a top view showing another embodiment of the functional film.
  • FIG. 2A shows a dot pattern in which the low-hardness portion 1 is a cylinder
  • FIG. 2B shows a pattern of a lattice (checkerboard pattern) in which the low-hardness portion 1 is a quadrangular column
  • FIG. 2C shows a low-hardness portion. 1 shows a pattern of a honeycomb structure in which a regular hexagonal column is used.
  • the size of the pattern is not particularly limited, but may be 100 nm or more, 1 ⁇ m or more, 100 ⁇ m or more, and 1 mm or more.
  • the upper limit of the size of the pattern is not particularly limited, but from the viewpoint of manufacturing, it may be 1 m or less or 10 mm or less.
  • the line width can be in the above range
  • the dot diameter can be in the above range
  • the resolution of the mask can be in the above range.
  • the size of the low hardness portion can be set according to the size of the article and the range in which the article is arranged. Further, from the viewpoint of the rigidity of the functional film, the size of the high hardness portion can be set.
  • the thickness of the functional film may be 0.1 ⁇ m or more, 1 ⁇ m or more, 10 ⁇ m or more, or 100 ⁇ m or more, and may be 100 mm or less, 100,000 ⁇ m or less, 10000 ⁇ m or less, or 1000 ⁇ m or less.
  • the functional film of the present embodiment can have selective adhesion to which the article selectively adheres to a low hardness portion.
  • the selective adhesion ratio calculated by the following evaluation method may be 60% or more, 70% or more, 80% or more, 90% or more, or 100%.
  • evaluation method A glass plate filled with acrylic beads having a particle size of 1.5 ⁇ m is pressed with a functional film at a pressure 1/100 times the storage elastic modulus of the low-hardness portion until the acrylic beads adhere to each other (acrylic beads on the low-hardness portion). If it is difficult for the acrylic beads to adhere to each other, gradually increase the pressing pressure until the acrylic beads adhere to each other).
  • the selective adhesion ratio for example, when a functional film is applied to the transport of metal particles, it becomes easy to arrange the metal particles in a specific part at a high density and the metal particles in other parts at a low density. This makes it possible to increase the conductivity of a specific portion.
  • the supporting base material examples include metal base materials such as SUS, gold, copper, aluminum, and alloys, silicone, silicon wafers, glass, polyethylene terephthalate (PET), triacetyl cellulose (TAC), and polyethylene naphthalate (PEN).
  • metal base materials such as SUS, gold, copper, aluminum, and alloys, silicone, silicon wafers, glass, polyethylene terephthalate (PET), triacetyl cellulose (TAC), and polyethylene naphthalate (PEN).
  • PMMA Polymethylmethacrylate
  • PC Polyethylene
  • PI Polyethylene
  • PE Polypropylene
  • PVA Polyvinyl Alcohol
  • PVC Polyvinyl Chloride
  • COC Cycloolefin Copolymer
  • COP Cycloolefin Polymer
  • norbornene resin containing, polyether sulfone, cellophane, aromatic polyamide, and a film of a combination thereof can be mentioned.
  • the functional film of the present embodiment may be laminated with a protective film.
  • the protective film include adhesive films such as rubber-based, acrylic-based, silicone-based, urethane-based, and fluorine-based.
  • the low hardness portion and the high hardness portion may be resin cured products, respectively.
  • the functional film of the present embodiment has a pattern of a first resin cured product having a storage elastic modulus of 0.01 MPa or more and a second resin having a storage elastic modulus higher than that of the first resin cured product. It may contain a pattern of a cured product.
  • the storage elastic modulus of the first cured resin product and the second cured resin product preferably satisfies the relationship between the storage elastic modulus and the storage elastic modulus of the low hardness portion and the high hardness portion described above.
  • the adhesive strength of the low-hardness portion is preferably higher than that of the high-hardness portion in order to increase the adhesiveness of the article to the low-hardness portion as compared with the high-hardness portion.
  • the adhesive strength of the low-hardness portion and the high-hardness portion can be appropriately adjusted by using the adhesive strength to the glass plate (glass adhesive strength) measured by the following method as an index. [Measurement of glass adhesive strength] Samples (thickness 100 ⁇ m, length 100 mm, width 25 mm) of the first unpatterned cured resin product (low hardness part) and the second cured resin product (high hardness part) were used as the first cured resin product (25 mm width).
  • the above sample is attached to a glass plate using a rubber roll at a pressure of 5880 N / m and a speed of 2 mm / min, and left at room temperature for 30 minutes. Then, the adhesive strength is measured with a tensile tester "HIMADZU, EZ-S" at a peeling angle of 180 degrees and a peeling speed of 0.3 m / min.
  • the adhesive strength of the low hardness portion may be more than 0 N / 25 mm, preferably 0.01 N / 25 mm or more, and 0.1 N / 25 mm or more. Is more preferable.
  • the upper limit of the glass adhesive force of the low hardness portion is not particularly limited, but for example, when the article is transported on the adhesive sheet, the adhesive force of the adhesive sheet is used in order to efficiently transfer the adhered article onto the adhesive sheet. It is desirable that it is lower than.
  • the adhesive strength of the high-hardness portion may be 1 N / 25 mm or less, and 0.1 N / 25 mm or less, from the viewpoint of selectively adhering the article to the low-hardness portion rather than the high-hardness portion. Is more preferable, and 0.01 N / 25 mm or less is more preferable.
  • the lower limit of the glass adhesive force of the high hardness portion is not particularly limited, but the glass adhesive force is preferably 0 N / 25 mm.
  • the functional film of the present embodiment can be produced, for example, by the following production method (i), production method (ii), production method (iii), or production method (iv).
  • Method (i) A step of preparing a curable composition which is in the form of a film and has photocurability (i-S1), and a step of exposing the first region and the second region of the curable composition as exposed portions (i-S2). ), And a step (i-S3) of exposing one of the first region and the second region of the curable composition as an exposed portion and the other as an unexposed portion.
  • the first resin cured product is between the step of applying the curable composition to the side where the pattern is provided (ii-S2) and the pattern of the first resin cured product by curing the curable composition.
  • a method comprising a step (ii-S3) of providing a second cured resin product having a hardness different from that of the above.
  • one region where exposure is repeated can be a high hardness region and the other region can be a low hardness region, and a functional film having these regions having different hardness can be obtained. it can.
  • the production method (ii) it is possible to obtain a functional film having a pattern of the first cured resin product and a second cured resin product provided between the patterns as the portions having different hardness.
  • the regions exposed to thermosetting and pattern can be defined as high hardness regions, and the regions not exposed by thermosetting can be designated as low hardness regions. It is possible to obtain a functional film having portions having different hardness.
  • a functional film having a portion where the pattern of the first curable composition is cured and a portion where the pattern of the second curable composition is cured is provided as a portion having different hardness.
  • the photocurable property means the property of being cured by irradiation with active energy rays such as infrared rays, visible rays, ultraviolet rays, and electron beams
  • the thermosetting property is the property of being cured by heating.
  • FIG. 3 is a schematic diagram for explaining the manufacturing method (i).
  • a step (i-S1) a film-like curable composition having photocurability (hereinafter, also referred to as a photocurable composition) is formed on the support base material 20 in the form of a film.
  • the photocurable composition 30 is provided.
  • the film-shaped photocurable composition 30 may be formed by applying a coating liquid of the photocurable composition on the support base material 20 and drying it, or a film-shaped photocurable composition prepared in advance. May be formed by laminating on the support base material 20.
  • the coating liquid may contain a solvent for the purpose of viscosity, coatability, thickness adjustment of the coating film, and the like.
  • the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; esters such as ethyl acetate and butyl acetate; alcohols such as isopropyl alcohol and ethyl alcohol; ethylene glycol monoethyl ether and ethylene glycol mono.
  • Polyhydric alcohol alkyl ethers such as butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether; benzene, toluene, xylene, methoxybenzene, 1, 2 -Aromatic hydrocarbons such as dimethoxybenzene; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene and chlorobenzene can be mentioned.
  • the solvent may be used alone or in combination of two or more.
  • a coating method of the coating liquid a normal coating method or a printing method can be applied. Specifically, for example, reverse coating, transfer roll coating, gravure roll coating, kiss coating, cast coating, spray coating, spin coating, dip coating, slot orifice coating, air doctor coating, bar coating, blade coating, dam coating, etc. And coatings such as die coating, and printing including jet printing, intaglio printing such as gravure printing, and stencil printing such as screen printing can be used.
  • Examples of the method for laminating the film-like composition include roll laminating, extrusion laminating, vacuum laminating and the like.
  • the thickness of the film-like photocurable composition 30 can be appropriately set so that the thickness of the above-mentioned functional film can be obtained.
  • the photocurable composition can contain a polymerizable compound (A) (hereinafter, also referred to as a component (A)) and a photopolymerization initiator (B) (hereinafter, also referred to as a component (B)).
  • A polymerizable compound
  • B photopolymerization initiator
  • component (A) a compound having a radically polymerizable functional group (hereinafter, also referred to as a component (A-1)) and a compound having a cationically polymerizable functional group (hereinafter, a component (A-2)). Also called).
  • Examples of the component (A-1) include compounds having a polymerizable unsaturated group.
  • Examples of the polymerizable unsaturated group include a carbon-carbon double bond such as a vinyl group (ethenyl group), an ethynyl group, an allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloylamino group.
  • Groups having As the component (A-1) one type can be used alone, or two or more types can be used in combination.
  • the photocurable composition contains a (meth) acryloyl group-containing monomer as the component (A-1).
  • the (meth) acryloyl group-containing monomer a monofunctional, bifunctional, or trifunctional or higher-functional monomer can be used.
  • Examples of the monofunctional (meth) acryloyl group-containing monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and butoxyethyl ().
  • Meta) acrylate isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate Meta) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-hydroxyethyl (Meta) acrylate, 2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate,
  • Cycloheptyl (meth) acrylate dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, mono (2- (meth) acryloyloxyethyl) tetrahydrophthalate, mono (2-( Examples thereof include alicyclic (meth) acrylates such as meta) acryloyloxyethyl) hexahydrophthalate, and EO-modified nonylphenol ethoxyacrylates.
  • bifunctional (meth) acryloyl group-containing monomer examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol.
  • trifunctional or higher functional (meth) acryloyl group-containing monomer examples include trimethyl propantri (meth) acrylate, ethoxylated trimethylol propanthry (meth) acrylate, propoxylated trimethylol propanthry (meth) acrylate, and ethoxylated propoxy.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a monovalent hydrocarbon group having a hydroxy group and having 2 to 10 carbon atoms].
  • Examples of the component (A-2) include a compound having a cyclic ether and a compound having a vinyl ether.
  • Examples of the cyclic ether include an oxylane ring, an oxetane ring, a tetrahydrofuran ring and the like.
  • Examples of commercially available compounds having a vinyl ether group include EHVE, HBVE, DEVGV, EHVE (manufactured by Maruzen Petrochemical Co., Ltd., product name), Crosmer U01 (manufactured by Nippon Carbide Industries, Ltd., product name) and the like.
  • the photocurable composition contains a hydroxyl group-terminated epoxidized polybutadiene compound as the component (A-2).
  • a hydroxyl-terminated epoxidized polybutadiene compound for example, a commercially available product such as Epolide PB3600 (manufactured by Daicel Corporation, product name) can be used.
  • the photocurable composition according to the present embodiment can contain a component (A-1) and a component (A-2).
  • the total content of the component (A-1) and the component (A-2) in the photocurable composition prevents the non-polymerizable component from bleeding out, and has a high hardness portion and a low hardness portion.
  • 80% by mass or more is preferable, 85% by mass or more is more preferable, and 90% by mass or more is further based on the total mass of the photocurable composition. preferable.
  • the total content of the component (A-1) and the component (A-2) is preferably 99% by mass or less, preferably 99% by mass or less, based on the total mass of the photocurable composition from the viewpoint of curability and stability. It is more preferably mass% or less, and further preferably 95 mass% or less.
  • the content ratio of the component (A-1) and the component (A-2) in the photocurable composition is (A-1) with respect to 100 parts by mass of the component (A-1) from the viewpoint of increasing the hardness of the high hardness portion.
  • A-2) The component is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more.
  • the content of the component (A-2) is preferably 10,000 parts by mass or less, preferably 1000 parts by mass, with respect to 100 parts by mass of the component (A-1). It is more preferably parts or less, and even more preferably 500 parts by mass or less.
  • the component (B) includes a photoradical polymerization initiator (B-1) (hereinafter, also referred to as (B-1) component) and a photocationic polymerization initiator (B-2) (hereinafter, (B-2) component). Also called).
  • B-1 photoradical polymerization initiator
  • B-2 photocationic polymerization initiator
  • the component (B-1) may be any compound that initiates photopolymerization by generating radicals by irradiation with active energy rays such as ultraviolet rays, and a known photoradical polymerization initiator can be used.
  • Examples of the component (B-1) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, and 2-hydroxy-2-methyl-2-phenyl.
  • Alkylphenone-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal; Benzophenone, 4-methylbenzophenone, 2-methylbenzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxy Benzophenone-based photopolymerization initiators such as benzophenone; and thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothiox
  • component (B-1) one type can be used alone, or two or more types can be used in combination.
  • the extinction coefficient at a wavelength of 405 nm is 7 mL / g ⁇ cm as the component (B-1). It is possible to include a photoradical polymerization initiator having an extinction coefficient of 38 mL / g ⁇ cm or more at a wavelength of 365 nm. Examples of such a photoradical polymerization initiator include commercially available photopolymerization initiators (Omnirad series and Omnicat series manufactured by IGM Resins) having an extinction coefficient (mL / g ⁇ cm in MeOH) shown in the table below, BASF. (Irgacure series manufactured by Sun Appro, CPI series manufactured by Sun Appro) can be used.
  • Examples of the component (B-2) include compounds capable of generating a substance that initiates cationic polymerization by irradiation with light.
  • an onium salt that generates Bronsted acid by light irradiation is preferable.
  • a diazonium salt of Bronsted acid an iodonium salt of Bronsted acid, and a sulfonium salt of Bronsted acid.
  • the cationic portion is an aromatic diazonium respectively, aromatic iodonium, aromatic sulfonium, anionic portion is BF 4 -, PF 6 -, SbF 6 -, [BX 4] - (X is at least two (Indicating a phenyl group substituted with fluorine or trifluoromethyl group), [PF n Y 6-n ] - (Y indicates a fluorinated alkyl group or a fluorinated phenyl group having 1 to 9 carbon atoms, n is 1 It is an onium salt composed of (an integer of ⁇ 6) and the like.
  • the cation moiety is preferably aromatic sulfonium or aromatic sulfonium, and more preferably aromatic sulfonium, from the viewpoint of photocurability.
  • Specific compounds include a phenyldiazonium salt of boron tetrafluoride, a diphenyliodonium salt of phosphorus hexafluoride, a triphenylsulfonium salt of phosphorus hexafluoride, and a triphenylsulfonium salt of tris (pentafluoroethyl) trifluorophosphate.
  • Examples thereof include a mixture of an aluminum salt and an orthonitrobenzylsilyl ether, a phenylthiopyridium salt, and a phosphorus allene hexafluoride-iron complex.
  • CD-1012 manufactured by SARTOMER, product name
  • PCI-019 PCI-021 (above, manufactured by Nippon Kayaku Co., Ltd., product name)
  • optomer SP-150 optomer SP-170 (above).
  • component (B-2) one type can be used alone, or two or more types can be used in combination.
  • the extinction coefficient at a wavelength of 405 nm is 5 mL / g ⁇ cm as the component (B-2).
  • a photocationic polymerization initiator having an extinction coefficient of 38 mL / g ⁇ cm or more at a wavelength of 365 nm can be contained.
  • a commercially available photopolymerization initiator having an extinction coefficient (mL / g ⁇ cm in MeOH) shown in the following table can be used.
  • the photocurable composition of the present embodiment preferably contains the above-mentioned component (A-1), component (A-2), component (B-1), and component (B-2). ..
  • the contents of the component (B-1) and the component (B-2) in the photocurable composition are appropriately set so that the storage elastic modulus of the high hardness portion and the low hardness portion is within a preferable range. be able to.
  • the total content of the component (B-1) is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, based on 100 parts by mass of the total of the component (A-1). It is preferable, and 1.0 part by mass or more is more preferable. Further, the total content of the component (B-1) is preferably 10 parts by mass or less, preferably 5 parts by mass, based on 100 parts by mass of the total of the component (A-1) from the viewpoint of preventing bleeding out of the unreacted component. The following is more preferable, and 3 parts by mass or less is further preferable.
  • the total content of the component (B-2) is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, based on 100 parts by mass of the total of the component (A-2). It is preferable, and more preferably 1 part by mass or more.
  • the total content of the component (B-2) is preferably 10 parts by mass or less, preferably 7.5 parts by mass, based on 100 parts by mass of the total component (A-2) from the viewpoint of stability when uncured. It is more preferably parts or less, and even more preferably 5 parts by mass or less.
  • the total content of the component (B-1) and the component (B-2) is 0.5 with respect to a total of 100 parts by mass of the component (A-1) and the component (A-2) from the viewpoint of reactivity. It is preferably parts by mass or more, more preferably 2 parts by mass or more, and even more preferably 4 parts by mass or more.
  • the total content of the ((B-1) component and the (B-2) component is 100 parts by mass in total of the (A-1) component and the (A-2) component from the viewpoint of stability when uncured. On the other hand, 15 parts by mass or less is preferable, 10 parts by mass or less is more preferable, and 7 parts by mass or less is further preferable.
  • the photocurable composition of the present embodiment may have an aliphatic amine compound (C) (hereinafter, also referred to as (C) component) and an aliphatic diol (D) (hereinafter, also referred to as (D) component), if necessary.
  • C aliphatic amine compound
  • D aliphatic diol
  • Antioxidant (E) hereinafter, also referred to as (E) component
  • ultraviolet absorber (F) hereinafter, also referred to as (F) component
  • other additives may be contained.
  • a known aliphatic amine compound can be used as the component (C). Above all, it is desirable to use an aliphatic tertiary amine having low nucleophilicity, and from the viewpoint of volatility, the total carbon number of the amine compound is preferably 10 or more.
  • Commercially available products of such aliphatic tertiary amines include dimethyloctylamine, tri (2-ethylhexyl) amine, trioctylamine, dimethyldecylamine, dimethyldodecylamine, dicyclohexylmethylamine, dimethylhexadecylamine, and dioctadecylmethyl. Amine and the like can be mentioned.
  • the component (C) in the photocurable composition, even when a small amount of the photocationic polymerization initiator is decomposed by light irradiation (for example, light having a wavelength of 405 nm), the cation polymerization is carried out by the generated acid. It can be suppressed from being started.
  • the content of the component (C) is preferably 20 parts by mass or less with respect to 100 parts by mass of the component (B-2) from the viewpoint of not inhibiting cationic polymerization.
  • 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol.
  • Known bifunctional aliphatic alcohols such as tricyclodecanedimethanol can be used.
  • the component (D) By including the component (D) in the photocurable composition, it becomes easy to expand the adjustment range of the hardness of the cured resin product. Further, when the portion of the cured resin product having different hardness is provided, it becomes easy to increase the difference in hardness.
  • the content of the component (D) is preferably 20 parts by mass or less with respect to 100 parts by mass of the component (A-2) from the viewpoint of maintaining the hardness of the high hardness portion.
  • a hindered phenol-based antioxidant a hindered amine-based light stabilizer, or the like can be used.
  • commercially available antioxidants such as IRGANOX1010, IRGANOX1035, IRGANOX1136, IRGANOX1520, TINUVIN292, and TINUVIN123 (above, manufactured by BASF, product name) may be used.
  • the component (E) By including the component (E) in the photocurable composition, it is possible to prevent the component (A-2) from being oxidized by heat and discoloring.
  • Examples of the component (F) include cyanoacrylate-based, dihydroxybenzophenone-based, benzotriazole-based, triazine-based, benzophenone-based, and benzoate-based ultraviolet absorbers.
  • Examples of these UV absorbers include Adekastab LA-32, Adekastab LA-38, Adekastab LA-36, Adekastab LA-34, Adekastab LA-31, Adekastab 1413, Adekastab LA-51, Adekastab LA-46, and Adekastab LA-F70.
  • UV absorbers such as 384-2, chinubin 460, chinubin 479, and chinubin 1577 (above, manufactured by BASF, product name) can be used.
  • the component (F) in the photocurable composition it becomes easy to improve the weather resistance and suppress the curing of the portion where the photocuring is unnecessary.
  • the photocurable composition of the present embodiment may contain various additives as needed.
  • additives for example, adhesion improvers such as coupling agents, polymerization inhibitors, light stabilizers, defoamers, fillers, chain transfer agents, thixotropy-imparting agents, flame retardants, mold release agents, surfactants, lubricants. , Antistatic agent and the like.
  • adhesion improvers such as coupling agents, polymerization inhibitors, light stabilizers, defoamers, fillers, chain transfer agents, thixotropy-imparting agents, flame retardants, mold release agents, surfactants, lubricants.
  • Known additives can be used as these additives.
  • step (i-S2) of exposing the first region and the second region of the curable composition as an exposed portion and the first region and the second region of the curable composition As a step (i-S3) of exposing one as an exposed portion and the other as an unexposed portion, the front surface of the film-like photocurable composition 30 is irradiated with light L1 ((a) in FIG. 3), and then the mask 53. Light L2 is irradiated through the film ((b) in FIG. 3).
  • the light source used for light irradiation is not particularly limited, and examples thereof include LED lamps, mercury lamps (low pressure, high pressure, ultra high pressure, etc.), metal halide lamps, excimer lamps, xenon lamps, and the like, preferably LED lamps and mercury lamps. Lamps, metal halide lamps, etc.
  • the exposure amount can be appropriately adjusted so that a predetermined reaction rate can be obtained in the film-like photocurable composition.
  • the exposure wavelength is not particularly limited, and may be different or the same in the steps (i-S2) and (i-S3). When the exposure wavelength is the same, the hardness of the cured resin product can be adjusted by adjusting the intensity of irradiation.
  • the film-like photocurable composition 30 contains (A-1) component, (A-2) component, (B-1) component, and (B-2) component, and is an LED of 405 nm as a light source of light L1.
  • a lamp can be used, and a 365 nm LED lamp can be used as the light source of the light L2.
  • the mask 53 may be an optical filter.
  • one region where the exposure is repeated can be designated as the high hardness region 2 and the other region can be designated as the low hardness region 1.
  • a functional film 10 having portions having different hardness can be obtained, and a functional film 110 with a support base material in which the functional film 10 is provided on the support base material 20 can be obtained.
  • the obtained functional film with a supporting base material is preferably stored so as not to be exposed to light until use.
  • FIG. 4 is a schematic diagram for explaining the manufacturing method (ii).
  • a patterned base material including the support base material 20 and the pattern 3 of the first cured resin product provided on the support base material 20 is prepared. ((A) in FIG. 4).
  • the pattern 3 of the first cured resin product can be formed, for example, by providing a film-like photosensitive composition on the support base material 20 and patterning the photosensitive composition by exposure and development.
  • the film-shaped photosensitive composition can be provided by laminating a film-shaped photosensitive composition prepared in advance, or by applying and drying the photosensitive composition.
  • the photosensitive composition can contain, for example, a polymerizable compound, a photopolymerization initiator, and other components if necessary, so that the desired hardness of the low hardness portion or the high hardness portion can be obtained.
  • a polymerizable compound and the photopolymerization initiator the same compounds as described above can be used.
  • a commercially available photosensitive film such as Fotec RD-2015, Fotec HM-40112, Raytec FZ-2700GA (all manufactured by Hitachi Chemical Co., Ltd., product name) can be used. ..
  • the thickness of the film-like photosensitive composition can be appropriately set so that the thickness of the above-mentioned functional film can be obtained.
  • the coating liquid of the curable composition is provided on the side where the pattern 3 of the first resin cured product of the patterned substrate is provided. Can be applied to provide the curable composition 40 between the patterns 3 of the first cured resin product.
  • the coating liquid may contain the above-mentioned solvent.
  • the photocurable composition can contain a polymerizable compound, a photopolymerization initiator, and other components if necessary.
  • a polymerizable compound and the photopolymerization initiator the same compounds as described above can be used.
  • the polymerizable compound contained in the photocurable composition may be monofunctional or polyfunctional.
  • thermosetting composition can contain a compound having a thermosetting functional group.
  • thermosetting functional group include a polymerizable unsaturated group, a carboxyl group, an epoxy group, a hydroxyl group, an isocyanate group, an amine group and a carbonate group. Two or more of these thermosetting functional groups may be contained in the compound.
  • the compound having a thermosetting functional group is not particularly limited as long as it has a thermosetting functional group, and may be a polymer compound having a thermosetting functional group, and a monomer having a thermosetting functional group. It may be a compound.
  • an acrylic resin having a functional group for example, a hydroxyl group
  • a thermal cross-linking agent is preferable.
  • thermosetting composition can further contain components such as a thermal polymerization initiator, a thermal crosslinker, and a reaction catalyst.
  • thermal polymerization initiator examples include azo compounds and peroxide compounds.
  • thermal cross-linking agent examples include a polyfunctional isocyanate compound, a polyfunctional hydroxyl group compound, a polyfunctional epoxy compound, a polyfunctional carboxyl group-containing compound, a polyfunctional amine compound, and a polyfunctional carbonate compound.
  • the photo- and thermosetting composition may contain the components exemplified by the photo-curable composition and the components exemplified by the thermosetting composition, and the photo-curable functional group and the thermosetting functional group may be used. It may contain a compound having the above in the molecule.
  • Examples of the compound having a photocurable functional group and a thermosetting functional group in the molecule include a photocurable functional group such as a (meth) acryloyl group and a vinyl group, and an epoxy group, a carboxyl group, a hydroxyl group, and a hydroxyl group. Examples thereof include compounds having both a thermosetting functional group such as an isocyanate group in the molecule.
  • Compounds having a carboxyl group and a photocurable functional group include dimer of (meth) acrylic acid and (meth) acrylic acid (for example, manufactured by Toa Synthetic Co., Ltd., trade name "Aronix M5600”), caprolactone modification (meth). ) Acrylic acid (for example, ⁇ -carboxy-polycaprolactone monoacrylate, manufactured by Toa Synthetic Co., Ltd., trade name "Aronix M5300”), a compound obtained by a ring-opening reaction between (meth) acrylate having a hydroxy group and carboxylic acid anhydride.
  • Examples of the compound having an isocyanate group and a photocurable functional group include methacryloyloxyethyl isocyanate (for example, manufactured by Showa Denko KK, trade name "Karenzu MOI").
  • Examples of the polymerizable compound having an epoxy group and a photocurable functional group include glycidyl (meth) acrylate and (meth) acrylate having an epoxy group such as 3,4-epoxycyclohexyl (meth) acrylate.
  • Examples of the compound having a hydroxy group and a photocurable functional group include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol triacrylate, and di. Hydroxyalkyl (meth) acrylates such as pentaerythritol pentaacrylate can be mentioned.
  • the compound having a photocurable functional group and a thermosetting functional group in the molecule has a polymerizable double bond on the side chain of the acrylic resin and thermosetting such as an epoxy group, a carboxyl group, a hydroxyl group and an isocyanate group. It may be a polymer compound (acrylic acrylate) having both a functional group. Examples of such a hydroxyl group-containing acrylic acrylate include Hitaroid 7988, Hitaroid 5990 (all manufactured by Hitachi Kasei Co., Ltd., trade name) and the like.
  • the coating liquid of the curable composition can be applied in the same manner as the above-mentioned coating method.
  • the curable composition is thermosetting and photocurable by heating when the curable composition is thermosetting, and by light irradiation when the curable composition is photocurable. If it is property, the curable composition 40 is cured by heating and / or light irradiation.
  • FIG. 4C shows a mode of irradiating light L.
  • the second resin cured product 4 having a hardness different from that of the first resin cured product during the pattern 3 of the first resin cured product.
  • a functional film 120 with a support base material 12 provided with the functional film 12 on the support base material 20 capable of forming the functional film 12 provided with the support base material 20 can be obtained.
  • FIG. 5 is a schematic diagram for explaining the manufacturing method (iii).
  • a curable composition having heat curability and photocurability hereinafter, also referred to as heat and photocurable composition
  • a film-like heat and photocurable composition 50 formed in a shape is provided.
  • the heat and photocurable composition the same one as the above-mentioned light and thermosetting composition can be used. Further, the film-like heat and photocurable composition 50 can be formed in the same manner as the above-mentioned film-like photocurable composition 30.
  • step (iii-S2) the entire film-like heat and photocurable composition 50 is heated and heat-cured, and then the heat-cured curable composition 52 is pattern-exposed. ..
  • the film-like heat and the photocurable composition 50 may be heated and pattern-exposed in this order, in the reverse order, or at the same time.
  • the region exposed to thermosetting and pattern is designated as the high hardness region 6 as the region having different hardness, and the region is thermoset and not exposed.
  • Can be set as a low hardness portion 5 a functional film 14 having portions having different hardnesses can be obtained, and a functional film with a support base material 14 is provided on the support base material 20. 130 is obtained.
  • the obtained functional film with a supporting base material is preferably stored so as not to be exposed to light until use.
  • the pattern of the first curable composition and the pattern of the second curable composition can be provided, for example, in the same manner as the above-mentioned coating method of the coating liquid.
  • the pattern of the first curable composition and the pattern of the second curable composition are subjected to the jet printing method from the viewpoint of the degree of freedom in pattern formation and the difference in hardness between the high hardness portion and the low hardness portion. It is preferable to provide it.
  • the coating liquids of the first curable composition and the second curable composition can be coated on the substrate in a predetermined pattern using an inkjet printer, respectively.
  • thermosetting composition As the first curable composition and the second curable composition, the above-mentioned photocurable composition, thermosetting composition, and light and thermosetting composition can be used, respectively.
  • the pattern of the first curable composition and the pattern of the second curable composition can be cured by heating and / or irradiating with light depending on the curable composition. it can.
  • the curing of the pattern of the first curable composition and the curing of the pattern of the second curable composition may be performed in this order, in the reverse order, or at the same time.
  • the first curable composition and the second curable composition are thermosetting compositions, and both patterns are heated at the same time, (b) the first curable composition and the first curable composition.
  • the second curable composition is a photocurable composition, and the pattern of the first curable composition is irradiated with light and the pattern of the second curable composition is irradiated with light in this order and vice versa.
  • the first curable composition is a thermosetting composition
  • the second curable composition is a photocurable composition
  • the first curable composition is heated.
  • the pattern of the second curable composition is irradiated with light in this order, in reverse order, or at the same time
  • the first curable composition is a thermosetting composition
  • the second The curable composition of No. 1 is a light and thermosetting composition, and heating of both patterns and irradiation of the pattern of the second curable composition with light are performed in this order, in reverse order, or at the same time. Can be done.
  • a functional film having a portion where the pattern of the first curable composition is cured and a portion where the pattern of the second curable composition is cured is provided as a portion having different hardness.
  • the obtained functional film is preferably stored so as not to be exposed to light until use.
  • the method of transporting the article of the present embodiment is a method of transporting the article on the base material onto another base material, the above-mentioned step of preparing the functional film according to the present embodiment, and the article on the base material. It includes a step of pressing the functional film into the first resin cured product to attach the article to the first resin cured product, and a step of transferring the article adhering to the first resin cured product onto another base material.
  • the method of transporting the article of the present embodiment will be described by taking as an example the case of using the functional film 10 having a checkered pattern in which the low hardness portion 1 is a quadrangular pillar shown in FIG. 6A.
  • the prepared functional film 10 is pressed against the article 70 arranged on the glass plate 60 so that the low hardness portion 1 is in contact with the article 70 ((b) in FIG. 6). By this pressing, the article 70 can be attached to the low hardness portion 1 ((c) in FIG. 6).
  • Examples of the article 70 include electronic parts, semiconductor materials, elements, chips, particles, cells, crystals, biomaterials, and the like.
  • the pressure for pressing the functional film can be such that the pressure between the low hardness part and the article is 1/100 times or more the storage elastic modulus of the low hardness part and less than the storage elastic modulus of the high hardness part. From the viewpoint of improving the selective adhesion to the low hardness part, the pressure at the time of pressing is 1/100 times or more of the storage elastic modulus of the low hardness part and 1/10 times or less of the storage elastic modulus of the high hardness part. It may be 1/100 times the storage elastic modulus of the low hardness portion. When the low-hardness portion has sufficient adhesiveness, the pressure between the low-hardness portion and the article can be 0.01 MPa or more regardless of the storage elastic modulus of the low-hardness portion. When pressing the functional film, the functional film may be heated if necessary.
  • the article can be conveyed by arranging the article 70 at a predetermined position on the adhesive sheet 80 from the functional film 10 to which the article 70 is attached (FIG. 6 (d)).
  • a known transfer device such as an adsorption transfer device may be used to move the functional film that picks up the article from the base material onto another base material.
  • the base material and another base material may be moved.
  • a glass plate and an adhesive sheet are used as the base material and another base material, but the base material and another base material are appropriately selected according to the type of the article and the type of transport work. can do.
  • the article can be efficiently removed from the functional film after transportation.
  • the functional film may be heated or cooled as needed, and the adhesive force between the low hardness portion and the article is lowered by a method such as irradiating the functional film with light from the side not in contact with the article. You may.
  • active energy rays such as infrared rays, visible rays, ultraviolet rays, and electron beams can be used.
  • the light source include LED lamps, mercury lamps (low pressure, high pressure, ultra high pressure, etc.), metal halide lamps, excimer lamps, xenon lamps, and the like. From the viewpoint of improving the efficiency of the curing reaction by light irradiation, it is preferable to irradiate light having a wavelength of 365 nm. In this case, a light source such as a 365 nm LED lamp, a high-pressure mercury lamp, or a metal halide lamp can be used.
  • the film-like curable composition of the present embodiment is used to form a functional film having the above-mentioned sites having different hardness.
  • the film-curable composition of the present embodiment can be used, for example, for forming the film-curable composition 30 in the production method (i) and the film-curable composition 50 in the production method (iii).
  • the film-curable composition of the present embodiment is a film-curable composition containing (i) a photoradical polymerization initiator and a compound having a thermosetting functional group and a radically polymerizable functional group, (ii).
  • the above-mentioned compounds can be used as each component to be blended in the film-like curable composition of the present embodiment.
  • the thickness of the film-like curable composition of the present embodiment can be appropriately set according to the thickness of the functional film to be formed.
  • the thickness of the film-like curable composition shall be 10 ⁇ m or more. It can be 100 ⁇ m or more, or 1000 ⁇ m or more.
  • the film-like curable composition of the present embodiment may have the following characteristics.
  • Example 1 ⁇ Making a functional film> (Example 1)
  • the curable composition obtained in Preparation Example 1 was coated on a 100 ⁇ m-thick PET film (manufactured by Toyobo Co., Ltd., trade name “Cosmo Shine A4300”) as a supporting base material with a coating film thickness of 100 ⁇ m using a comma coater. Then, a film-like curable composition was formed.
  • the film-like curable composition is irradiated with LED light of 405 nm at an irradiation amount of 2000 mJ / cm 2 , and then LED light of 365 nm is irradiated at 2000 mJ / cm 2 through a mask having a stripe pattern with a line width of 50 ⁇ m / 50 ⁇ m. Irradiation was performed to form a functional film on the supporting substrate.
  • the portion irradiated with the LED light of 365 nm was a high hardness portion.
  • Example 2 A film-like curable composition was formed on the supporting substrate in the same manner as in Example 1 except that the curable composition obtained in Preparation Example 2 was used. This was heated at 100 ° C. for 10 minutes, then cured at 40 ° C. for 3 days, and then irradiated with the light of a high-pressure mercury lamp at an irradiation amount of 1000 mJ / cm 2 through a mask having a striped pattern with a line width of 50 ⁇ m / 50 ⁇ m. A functional film was formed on the supporting substrate.
  • the part irradiated with the light of the high-pressure mercury lamp was a high-hardness part.
  • Example 3 A film-like curable composition was formed on the supporting substrate in the same manner as in Example 1 except that the curable composition obtained in Preparation Example 3 was used. This was heated at 100 ° C. for 10 minutes, then cured at 40 ° C. for 3 days, and then irradiated with the light of a high-pressure mercury lamp at an irradiation amount of 1000 mJ / cm 2 through a mask having a striped pattern with a line width of 50 ⁇ m / 50 ⁇ m. A functional film was formed on the supporting substrate.
  • the part irradiated with the light of the high-pressure mercury lamp was a high-hardness part.
  • Example 4 A photosensitive film (manufactured by Hitachi Kasei Co., Ltd., product name "Fotech HM-60100", photoresist) on a PET film (manufactured by Toyo Boseki Co., Ltd., trade name "Cosmo Shine A4300”) with a thickness of 100 ⁇ m as a supporting base material.
  • a photosensitive film manufactured by Hitachi Kasei Co., Ltd., product name "Fotech HM-60100", photoresist
  • PET film manufactured by Toyo Boseki Co., Ltd., trade name "Cosmo Shine A4300”
  • the obtained functional film had a high hardness part in the resist pattern.
  • Example 5 The curable composition obtained in Preparation Example 5 and the curable composition obtained in Preparation Example 6 using an inkjet printing machine on a PET film having a thickness of 100 ⁇ m (manufactured by Toyobo Co., Ltd., trade name “Cosmo Shine A4300”) as a supporting base material.
  • the obtained curable composition was coated so as to form a stripe pattern having a coating film thickness of 10 ⁇ m and a line width of 50 ⁇ m / 50 ⁇ m, respectively, to form a film-like curable composition on a supporting substrate. This was heated at 100 ° C. for 10 minutes and then cured at 40 ° C. for 3 days to form a functional film on the supporting substrate.
  • the cured product of the curable composition obtained in Preparation Example 5 had a high hardness portion.
  • Example 6 A film-like curable composition was formed on the supporting substrate in the same manner as in Example 5 except that the curable composition obtained in Preparation Example 4 and the curable composition obtained in Preparation Example 6 were used. did. This was heated at 100 ° C. for 10 minutes, then cured at 40 ° C. for 3 days, and then the pattern of the curable composition obtained in Preparation Example 4 was irradiated with the light of a high-pressure mercury lamp at an irradiation amount of 1000 mJ / cm 2. A functional film was formed on the supporting base material.
  • the cured product of the curable composition obtained in Preparation Example 4 had a high hardness portion.
  • the curable composition obtained in Preparation Example 3 was coated on a 100 ⁇ m-thick PET film (manufactured by Toyobo Co., Ltd., trade name “Cosmo Shine A4300”) as a supporting base material with a coating film thickness of 100 ⁇ m using a comma coater. Then, a film-like curable composition was formed. This was heated at 100 ° C. for 10 minutes, then cured at 40 ° C. for 3 days, and then the entire surface was irradiated with the light of a high-pressure mercury lamp at an irradiation amount of 1000 mJ / cm 2 to form a functional film on the supporting substrate. ..
  • the indentation elastic modulus (storage elastic modulus) by the nanoindenter method was measured under the following conditions, and the hardness of the minute part of the low hardness part and the high hardness part was evaluated.
  • Measuring equipment Nano indenter (BRKER, "TI 980 Tribo Indicator"
  • Measuring head Standard (1D) Transducer and Piezo Scanner Indenter: Berkovich (tip: diamond)
  • Adhesion selection ratio The adhesion selection ratio of the functional film was calculated according to the following evaluation method.
  • a functional film is placed on a glass plate filled with acrylic beads (manufactured by Soken Kagaku Co., Ltd., "MX-150") having a particle size of 1.5 ⁇ m. Pressed with a pressure of / 100 times (however, Comparative Example 1 was 1.5 MPa). Then, the functional film was lifted, and the area where the acrylic beads were attached to each of the low hardness portion and the high hardness portion (projected area of the beads on the film surface) was measured. Based on these areas and the areas of the low hardness part and the high hardness part, the selective adhesion ratio (%) was calculated according to the following formula.

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  • Polymers & Plastics (AREA)
  • Toxicology (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un film fonctionnel 10 qui a des parties de dureté différente et comprend un motif 1 d'un premier produit durci de résine qui a un module de stockage d'au moins 0,01 MPa et un motif 2 d'un second produit durci de résine qui a un module de stockage supérieur à celui du premier produit durci de résine.
PCT/JP2020/044895 2019-12-05 2020-12-02 Film fonctionnel, composition durcissable de type film, procédé de production de film fonctionnel et procédé de transport d'article WO2021112132A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2019220609 2019-12-05
JP2019-220609 2019-12-05
JP2020081981A JP2021091855A (ja) 2019-12-05 2020-05-07 機能性フィルム、フィルム状硬化性組成物及び機能性フィルムの製造方法
JP2020-081981 2020-05-07

Publications (1)

Publication Number Publication Date
WO2021112132A1 true WO2021112132A1 (fr) 2021-06-10

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PCT/JP2020/044895 WO2021112132A1 (fr) 2019-12-05 2020-12-02 Film fonctionnel, composition durcissable de type film, procédé de production de film fonctionnel et procédé de transport d'article

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WO (1) WO2021112132A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7456269B2 (ja) 2020-05-07 2024-03-27 株式会社レゾナック マイクロｌｅｄチップ搬送用フィルム及びマイクロｌｅｄチップの搬送方法
WO2024194531A1 (fr) * 2023-03-21 2024-09-26 Teknologian Tutkimuskeskus Vtt Oy Film biodégradable et son procédé de fabrication

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150144913A1 (en) * 2013-11-28 2015-05-28 Samsung Display Co., Ltd. Adhesive film and manufacturing method of the same, and display device including the adhesive film
KR20170001102A (ko) * 2015-06-25 2017-01-04 동우 화인켐 주식회사 패턴화된 하드코팅 필름
WO2017119391A1 (fr) * 2016-01-08 2017-07-13 大日本印刷株式会社 Film optique, plaque polarisante et dispositif d'affichage d'image
KR20190102872A (ko) * 2018-02-27 2019-09-04 도레이첨단소재 주식회사 이종기재 접합용 양면 점착필름, 적층필름 및 디스플레이 디바이스
WO2019202749A1 (fr) * 2018-04-16 2019-10-24 株式会社寺岡製作所 Ruban adhésif sensible à la pression

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150144913A1 (en) * 2013-11-28 2015-05-28 Samsung Display Co., Ltd. Adhesive film and manufacturing method of the same, and display device including the adhesive film
KR20170001102A (ko) * 2015-06-25 2017-01-04 동우 화인켐 주식회사 패턴화된 하드코팅 필름
WO2017119391A1 (fr) * 2016-01-08 2017-07-13 大日本印刷株式会社 Film optique, plaque polarisante et dispositif d'affichage d'image
KR20190102872A (ko) * 2018-02-27 2019-09-04 도레이첨단소재 주식회사 이종기재 접합용 양면 점착필름, 적층필름 및 디스플레이 디바이스
WO2019202749A1 (fr) * 2018-04-16 2019-10-24 株式会社寺岡製作所 Ruban adhésif sensible à la pression

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7456269B2 (ja) 2020-05-07 2024-03-27 株式会社レゾナック マイクロｌｅｄチップ搬送用フィルム及びマイクロｌｅｄチップの搬送方法
WO2024194531A1 (fr) * 2023-03-21 2024-09-26 Teknologian Tutkimuskeskus Vtt Oy Film biodégradable et son procédé de fabrication

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