WO2019131597A1 - Copolymère acrylique séquencé et film antibuée en contenant - Google Patents

Copolymère acrylique séquencé et film antibuée en contenant Download PDF

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Publication number
WO2019131597A1
WO2019131597A1 PCT/JP2018/047493 JP2018047493W WO2019131597A1 WO 2019131597 A1 WO2019131597 A1 WO 2019131597A1 JP 2018047493 W JP2018047493 W JP 2018047493W WO 2019131597 A1 WO2019131597 A1 WO 2019131597A1
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block copolymer
block
antifogging
hydrophilic
hydrophobic
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PCT/JP2018/047493
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English (en)
Japanese (ja)
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健太郎 西井
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株式会社ネオス
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Priority to JP2019561698A priority Critical patent/JP7239490B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to an acrylic block copolymer and an antifogging film comprising the same.
  • the antifogging film is, for example, a) a window glass of a building structure, a car, etc. b) a mirror surface of a bathroom or vanity stand, c) a lens or lens cover such as glasses, goggles or face mask, d) Various types of lighting, covers for lighting, such as headlights, e) displays, covers for monitors, etc. f) fogging (diffuse reflection of light) due to condensation such as glass surfaces such as cold storage showcases or transparent resin surfaces It is used for the part / member to be obtained.
  • the principle of antifogging for example, 1) a method of modifying surface wetting, 2) a method by water absorption, 3) a method by water repellency, 4) a method by temperature control, etc. are known.
  • the method by water absorption in the above 2) is superior to other methods in that the antifogging effect has high durability.
  • the method by water absorption by coating a hydrophilic polymer film on the substrate surface, water can be absorbed by the film surface, so that the formation of water droplets can be suppressed on the surface. As a result, a sustained antifogging effect can be exhibited.
  • water absorption type antifogging films those using various polymer materials have been developed.
  • An article with an antifogging film is known in which the inorganic composite antifogging film contains the water-absorbent resin as a main component, and the organic-inorganic composite antifogging film further contains an ultraviolet light absorber and / or an infrared light absorber. ).
  • an antifogging article having a substrate and a water absorbing layer containing a crosslinked resin disposed on the surface of the substrate, wherein the water absorbing layer contains metal oxide fine particles in a proportion of 20 to 60% by mass.
  • an antifogging article characterized by containing and having a haze value of 1% or less (Patent Document 2).
  • the conventional antifogging film can exhibit a predetermined antifogging property as an initial performance, there is a problem that the antifogging property tends to decrease with time.
  • the water absorption type anti-fog film is composed of a hydrophilic component, the hydrophilic component separates from the anti-fog film to cause performance degradation. That is, when the hydrophilic component is dropped from the antifogging film, the water absorption is reduced, and it becomes difficult to maintain the antifogging property.
  • the main object of the present invention is to provide an antifogging film capable of continuously exhibiting excellent antifogging properties and an acrylic block copolymer for forming the same.
  • the present inventor has found that the above object can be achieved by adopting a composition having a specific composition, and has completed the present invention.
  • the present invention relates to the following acrylic block copolymer and an antifogging film comprising the same.
  • a block copolymer comprising a repetition of a hydrophilic block and a hydrophobic block, wherein (1) The solubility parameter of the monomer constituting the hydrophobic block is less than 10 [cal / cm 2 ] 1/2 and the solubility parameter of the monomer constituting the hydrophilic block is 10 [cal / cm 2 ] 1/2 or more
  • the hydrophobic block is an acrylic polymer having a glass transition temperature of 50 ° C. or less Acrylic block copolymer characterized in that.
  • Acrylamide-based polymers have the following general formula A: (Wherein R, R 1 and R 2 are the same or different and each represents a hydrogen atom or an alkyl group having 5 or less carbon atoms), which is a polymer of an acrylamide-based monomer Acrylic block copolymer. 4. The acrylic block copolymer according to Item 1, wherein the ratio of the hydrophilic block and the hydrophobic block is from 20:80 to 80:20 on the basis of a total of 100 mol% of the two. 5. 5.
  • a resin composition for forming an antifogging film comprising the acrylic block copolymer according to any one of the items 1 to 4. 6. 6.
  • the antifogging film-forming resin composition according to item 5 which contains an organic solvent and is liquid in nature. 7.
  • An antifogging film comprising the acrylic block copolymer according to any one of items 1 to 4.
  • An antifogging product comprising the antifogging film according to item 7 or 8 formed on the surface of an article.
  • the antifogging film which can exhibit the outstanding antifogging property continuously, and the acryl-type block copolymer for forming it can be provided.
  • the acrylic block copolymer of the present invention contains a specific hydrophobic block and a hydrophilic block, it is preferable to use an antifogging film containing a hydrophilic portion by a hydrophilic block and a hydrophobic portion by a hydrophobic block. It can be formed.
  • the antifogging film according to the present invention can exhibit excellent water absorption continuously. The mechanism of action is not clear, but it exerts excellent water absorption especially in the hydrophilic part, so it can rapidly absorb fine water droplets on the surface of the antifogging film, and the hydrophobic part has the function of supporting the hydrophilic part. It is considered that because it effectively suppresses or prevents the falling off from the antifogging film due to water absorption.
  • the acrylic block copolymer and the antifogging film of the present invention having such characteristics can be suitably used for various products which are required to have antifogging properties.
  • a building structure a window glass of a car, b) a mirror surface of a bathroom or vanity, c) a lens or lens cover such as glasses, goggles or face mask, d) a lighting cover such as various lights or headlights
  • a lighting cover such as various lights or headlights
  • It can be applied to a display device, a cover such as a monitor, f) a glass surface such as a cold storage showcase or a transparent resin surface.
  • the measurement result (The magnification of 120000 times, a bright part: CHA, a dark part: DMAA) of the transmission electron microscope in Example 1 is shown.
  • the acrylic block copolymer of the present invention (the copolymer of the present invention) is a block copolymer comprising a repetition of a hydrophilic block and a hydrophobic block, (1)
  • the solubility parameter of the monomer constituting the hydrophobic block is less than 10 [cal / cm 2 ] 1/2 and the solubility parameter of the monomer constituting the hydrophilic block is 10 [cal / cm 2 ] 1/2 or more
  • the hydrophobic block is an acrylic polymer having a glass transition temperature of 50 ° C. or less It is characterized by
  • acrylate or methacrylate is generically referred to as "(meth) acrylate”
  • acrylic acid or methacrylic acid is generically referred to as “(meth) acrylic acid”, unless otherwise specified.
  • the monomer constituting the hydrophobic block (polymer) has a solubility parameter (hereinafter also referred to as “SP value”) of less than 10 [cal / cm 2 ] 1/2 , preferably 9.8 [cal / cm 2 ]. It is 1/2 or less, more preferably 9.5 [cal / cm 2 ] 1/2 or less. Although the lower limit value of the SP value is not limited, it is usually about 7 [cal / cm 2 ] 1/2 .
  • the SP value in the present invention may be either a literature value or an actual measurement value, but it is desirable to adopt an actual measurement value when the two are significantly different.
  • the actual values can be measured according to known methods.
  • a sample usually a polymer
  • 20 kinds of solvents acetone, methylcyclohexane, methyl ethyl ketone, tetrahydrofuran, metaxylene hexafluoride, HFE-7100 (hydrofluoroether), dimethyl sulfoxide, diethylene glycol, N-methylpyrrolidone, acetonitrile, Conduct a solubility test to determine if it is soluble in 2-propanol, 2- (2-ethoxyethoxy) ethanol, toluene, diiodomethane, acetophenone, benzaldehyde, acetic acid, 2-ethylhexanol, propylene carbonate, ethanol) Construct SP spheres (Hansen'
  • an acrylic polymer preferably an acrylic polymer (with the exception of the acrylamide polymer) can be exemplified.
  • the acrylic polymer as the hydrophobic block preferably has a glass transition point (Tg) of 50 ° C. or less, more preferably 30 ° C. or less, and most preferably 20 ° C. or less. preferable. Thereby, higher water absorption can be obtained.
  • the lower limit value of the glass transition point is not particularly limited, but in general, it may be about ⁇ 70 ° C. (particularly about ⁇ 65 ° C.).
  • an acrylic polymer as a hydrophobic block refers to the homopolymer when it is assumed that a homopolymer is formed by the monomers constituting the hydrophobic block. Therefore, the glass transition point in the present invention refers to the glass transition point (literature value) of the homopolymer.
  • the glass transition point of the hydrophobic block is 15 ° C., which is the glass transition point of the homopolymer of cyclohexyl acrylate.
  • the glass transition point of a homopolymer is described as the glass transition point of the monomer which comprises it.
  • the monomer constituting the hydrophilic block has a solubility parameter of 10 [cal / cm 2 ] 1/2 or more, preferably 10.2 [cal / cm 2 ] 1/2 or more, more preferably 10.4 [cal / cm 2 ] 1/2 or more.
  • the upper limit value of the SP value is not limited, it may be normally about 13 [cal / cm 2 ] 1/2 .
  • an acrylamide type polymer can be used suitably, for example. Therefore, for example, the following general formula A: (However, R, R 1 and R 2 are the same or different and each represents a hydrogen atom or an alkyl group having 5 or less carbon atoms.) A polymer of an acrylamide-based monomer can be suitably used.
  • monomers in which R, R 1 and R 2 are the same or different from each other and are a hydrogen atom or an alkyl group having 2 or less carbon atoms are preferable.
  • monomers in which R is a hydrogen atom or a methyl group, and R 1 and R 2 are the same as each other and are a methyl group or an ethyl group are more preferable. Therefore, for example, N, N-dimethyl acrylamide or N, N-diethyl acrylamide can be suitably used as a monomer constituting the polymer of the hydrophilic block. Also in the hydrophilic block, it is desirable to be composed of one kind of monomer selected from these monomers.
  • the ratio of the hydrophobic block to the hydrophilic block can be appropriately set according to the desired antifogging property and the like. For example, it is desirable to set the ratio of the monomer constituting the hydrophobic block to the monomer constituting the hydrophilic block to be 20:80 to 80:20 based on the total 100 mol% of the both, and further 40:60. It is more desirable to set so as to be ⁇ 60: 40.
  • the block copolymer of the present invention as a result of being able to arrange the hydrophilic part by the hydrophilic block and the hydrophobic part by the hydrophobic block relatively uniformly, it is possible to more reliably maintain the better antifogging property Become.
  • functions such as thermosetting and photocuring
  • a reactive group for example.
  • a reactive group a hydroxyl group, a carboxyl group, an amino group, a formyl group, a carbonyl group, an epoxy group, an isocyanate group etc. are mentioned, for example. This can be produced by using a monomer having a reactive group as a raw material.
  • the reactive group may be introduced as a monomer constituting the hydrophobic block, or may be introduced as a monomer constituting the hydrophilic block.
  • the hydrophobic block or the hydrophilic block be composed of a homopolymer having one type of monomer having a reactive group as a monomer unit.
  • the SP value of the monomer is less than 10 [cal / cm 2 ] 1/2 , preferably 9.8 [cal / cm 2 ]. It is 1/2 or less, more preferably 9.5 [cal / cm 2 ] 1/2 or less. Although the lower limit value of the SP value is not limited, it is usually about 7 [cal / cm 2 ] 1/2 .
  • the SP value of the monomer is 10 [cal / cm 2 ] 1/2 or more, preferably 10.2 [cal / cm 2 ]. It is 1 ⁇ 2 or more, more preferably 10.4 [cal / cm 2 ] 1 ⁇ 2 or more.
  • the upper limit value of the SP value is not limited, it is usually about 13 [cal / cm 2 ] 1/2 .
  • the property (form) of the block copolymer of the present invention is not limited, but in general, it is preferably in the form of liquid (in particular, a solution in which the block copolymer is dissolved). Therefore, in this case, an organic solvent may be used.
  • organic solvent examples include ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate and methoxypropyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; diethyl ether, dibutyl ether, tetrahydrofuran, propylene glycol Various organic solvents such as ether solvents such as monomethyl ether acetate and diethylene glycol dimethyl ether, aromatic solvents such as toluene and xylene, and alcohol solvents such as methanol, ethanol and isopropyl alcohol can be used.
  • an organic solvent capable of dissolving the block copolymer of the present invention for example, at least one of a ketone solvent and an ester solvent
  • an organic solvent capable of dissolving the block copolymer of the present invention for example, at least one of a ketone
  • the amount of the organic solvent used is not limited.
  • the type of block copolymer to be used and the desired solid content in the range of 1 to 60% by weight (particularly 5 to 40% by weight) may be set appropriately according to the viscosity of the
  • the method for producing an acrylic block copolymer of the present invention is, for example, (1) a first step of preparing a first polymer constituting a hydrophobic block or a hydrophilic block, (2) A second step of obtaining an acrylic block copolymer composed of the first polymer and the second polymer while preparing the second polymer constituting the hydrophilic block or the hydrophobic block in the presence of the first polymer; It can manufacture by the method of including.
  • any of a) a method of forming a hydrophilic block after forming a hydrophobic block, b) a method of forming a hydrophobic block after forming a hydrophilic block, and the like are included.
  • the method a) is described as a representative example, but the method b) is also performed according to the method a) (the order of the first step and the second step is reversed). be able to.
  • the first polymer constituting the hydrophobic block is prepared.
  • the 1st polymer which comprises a hydrophobic block it is preferable to prepare an acryl-type polymer as a 1st polymer as shown above.
  • methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, tert-butyl (meth) acrylate, normal hexyl ( Meta) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate etc. can be used suitably.
  • the monomer which has a reactive group can also be used as a monomer.
  • a monomer having one or more hydroxyl groups as a reactive group can be suitably used.
  • a monomer having a hydroxyl group can crosslink the block copolymer by using a crosslinking agent such as an isocyanate compound in combination, and as a result, it is possible to provide an antifogging film having higher film strength.
  • a crosslinking agent such as an isocyanate compound in combination
  • Monomers having other reactive groups can also be used appropriately as long as the effects of the present invention are not impaired.
  • the monomer having a reactive group is also required to satisfy a predetermined SP value.
  • the monomer having a reactive group may also be selected to have an SP value of less than 10 [cal / cm 2 ] 1/2 .
  • one having an SP value of 10 [cal / cm 2 ] 1/2 or more may be selected.
  • the kind of crosslinking agent is not specifically limited, When using what has a hydroxyl group as said monomer, an isocyanate type compound can be used suitably. More specifically, for example, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate and the like can be mentioned. A commercial item can also be used for these crosslinking agents.
  • ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate and methoxypropyl acetate
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • organic solvents such as ether solvents such as monomethyl ether acetate and diethylene glycol dimethyl ether, aromatic solvents such as toluene and xylene, and amide solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc) and diethylformamide Can.
  • additives such as a polymerization initiator (thermal polymerization initiator) and a RAFT reagent, can also be mix
  • a thermal polymerization initiator for example, an azo compound such as dimethyl 2,2′-azobis (2-methylpropionic acid), 2,2′-azobisbutyronitrile, a peroxide such as benzoyl peroxide, etc. are used. be able to.
  • the RAFT reagent for example, 2-cyano-2-propyldodecyltrithiocarbonate can be used.
  • reaction conditions in the liquid phase are not particularly limited.
  • the reaction temperature may be appropriately set within the range of about 40 to 90 ° C.
  • the reaction time may be within the range of about 1 to 15 hours.
  • the first polymer can be prepared.
  • an acrylic block copolymer composed of the first polymer and the second polymer is obtained while preparing the second polymer constituting the hydrophilic block in the presence of the first polymer.
  • the second polymer it is preferable to prepare an acrylamide-based polymer as described above. Therefore, as the monomer, a monomer represented by the above general formula A can be suitably used. In particular, for example, N, N-dimethyl acrylamide or N, N-diethyl acrylamide can be suitably used as a monomer (raw material) constituting the polymer of the hydrophilic block.
  • a monomer constituting a hydrophilic block a monomer having a reactive group (particularly, an acrylamide monomer) can be appropriately used within the range not to impair the effect of the present invention, similarly to the monomer constituting a hydrophobic block. .
  • the solvent is not particularly limited.
  • ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate and methoxypropyl acetate
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • diethyl ether, dibutyl ether Ether solvents such as tetrahydrofuran, propylene glycol monomethyl ether acetate and diethylene glycol dimethyl ether
  • aromatic solvents such as toluene and xylene
  • amide solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc) and diethylformamide.
  • Organic solvents can be used.
  • additives such as a polymerization initiator (thermal polymerization initiator) and a RAFT reagent, can also be mix
  • a thermal polymerization initiator for example, an azo compound such as dimethyl 2,2′-azobis (2-methylpropionic acid), 2,2′-azobisbutyronitrile, a peroxide such as benzoyl peroxide, etc. are used. be able to.
  • the RAFT reagent for example, 2-cyano-2-propyldodecyltrithiocarbonate can be used.
  • reaction conditions in the liquid phase are not particularly limited.
  • the reaction temperature may be appropriately set within the range of about 40 to 90 ° C.
  • the reaction time may be within the range of about 1 to 15 hours.
  • the acrylic block copolymer as the reaction product may be recovered.
  • the recovery method is not particularly limited. For example, (a) a step of preparing a solution by dissolving a reaction product in an organic solvent, (b) an acrylic block copolymer by mixing a poor solvent with the solution. It can be carried out by a method comprising the steps of forming a precipitate, and (c) recovering the precipitate by solid-liquid separation.
  • the solution is prepared by dissolving the reaction product in an organic solvent.
  • the organic solvent is not limited as long as it can dissolve the acrylic block copolymer which is the reaction product.
  • alcohol solvents such as methanol, ethanol, isopropyl alcohol, 1-propanol, 1-butanol, ethyl acetate Ester solvents such as butyl acetate, methoxybutyl acetate and methoxypropyl acetate; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; diethyl ether, dibutyl ether, tetrahydrofuran, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether and the like
  • organic solvents such as ether solvents, aromatic solvents such as toluene and xylene, and hydrocarbon solvents such as normal hexane and cyclo
  • the concentration of the solution is not particularly limited, and can be appropriately set, for example, in the range of about 1 to 60% by weight (preferably 5 to 40% by weight) according to the type of reaction product and the like.
  • the poor solvent may be appropriately selected according to the type of solvent (good solvent) used in the reaction.
  • a low polar solvent hydrocarbon solvent, aromatic solvent or the like
  • an ether solvent or the like is used as a solvent
  • an alcohol solvent or the like can be used as a poor solvent.
  • the mixing amount of the poor solvent is not limited, and may be an amount sufficient to precipitate almost all of the acrylic block copolymer contained in the solution.
  • the precipitate is recovered by solid-liquid separation.
  • the solid-liquid separation method is not particularly limited, and may be, for example, according to a known method such as pressure filtration or centrifugation.
  • the obtained acrylic block copolymer may be subjected to a drying treatment and the like as necessary.
  • the present invention includes an antifogging film containing an acrylic block copolymer and an antifogging product in which the antifogging film is laminated on the surface of an article.
  • the antifogging film of the present invention contains the acrylic block copolymer of the present invention.
  • the acrylic block copolymer of the present invention has a function of self assembly (phase separation). Therefore, when forming a film using an acrylic block copolymer, as a result of forming a film in a phase-separated state, a self-assembled film having a hydrophilic part by a hydrophilic block and a hydrophobic part by a hydrophobic block is formed. Be done. As a result, not only excellent antifogging properties can be exhibited initially but also antifogging properties can be exhibited continuously.
  • the acrylic block copolymer of the present invention is contained in an amount of about 95 to 100% by weight in the antifogging film (particularly 99 100% by weight) is preferably included.
  • the structure composed of the hydrophilic part by the hydrophilic block and the hydrophobic part by the hydrophobic block generally takes various forms depending on the volume ratio of the both, but may be any form.
  • a structure (cylindrical structure) dispersed in a matrix consisting of (or hydrophilic portions), a c-like structure in which plate-like hydrophilic portions and plate-like hydrophobic portions are alternately arranged (alternate lamella structure), and the like can be mentioned.
  • TEM transmission electron microscope
  • the hydrophobic portion is mainly composed of an acrylic polymer
  • the hydrophilic portion is mainly composed of an acrylamide polymer.
  • fine water droplets attached to the surface of the antifogging film can be absorbed, so that excellent antifogging properties can be exhibited.
  • the hydrophobic part since it plays a role of supporting and fixing the hydrophilic part, it is possible to effectively suppress the detachment of the hydrophilic part from the antifogging film by water, and as a result, the excellent antifogging property is sustained. It becomes possible.
  • the antifogging film of the present invention maintains excellent antifogging properties because it is a self-assembled film (phase separation film) composed of a hydrophobic portion containing an acrylic polymer and a hydrophilic portion containing an acrylamide polymer. It becomes possible. In the random structure (homogeneous structure), the desired water absorption performance can not be obtained unless the proportion of the polymer (acrylamide type polymer) constituting the hydrophilic part is large. On the other hand, when the phase separation is performed, the acrylamide polymer is present together to a certain extent (without being uniformly and finely dispersed), so that the water absorption performance is easily exhibited even if the molar ratio is relatively small. Also in the antifogging film of the present invention, since it has a phase-separated structure, excellent water absorption can be exhibited continuously.
  • the antifogging film of the present invention has a structure in which the hydrophilic part and the hydrophobic part are phase-separated, so that the hydrophobic part plays the role of preventing the dropout of the hydrophilic part. You can expect.
  • the thickness of the antifogging film can be appropriately set depending on the application, desired antifogging property, etc., usually in the range of about 1 to 900 ⁇ m (particularly 5 to 500 ⁇ m), but is not limited thereto.
  • the method for forming the antifogging film of the present invention is not particularly limited, and for example, by a method including the step of drying after forming a coating film by a coating liquid in which the acrylic block copolymer of the present invention is dissolved in a solvent. It can be implemented.
  • the preparation of the coating solution can be carried out by dissolving or dispersing the acrylic block copolymer of the present invention in a suitable solvent.
  • the solvent is not particularly limited, and examples thereof include ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate and methoxypropyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; diethyl ether, dibutyl ether, Various organic solvents such as ether solvents such as tetrahydrofuran, propylene glycol monomethyl ether acetate and diethylene glycol dimethyl ether, aromatic solvents such as toluene and xylene, alcohol solvents such as methanol, ethanol, isopropyl alcohol, 1-propanol and 1-butanol A solvent can be used.
  • the concentration of the coating solution can be appropriately set according to the type of acrylic block copolymer to be used, the desired viscosity of the coating solution, etc., but usually about 1 to 60% by weight (preferably 5 to 40%) It should be in the range of%).
  • the method of forming the coating film is not particularly limited, and for example, a) after forming a coating film on a support, the antifogging film obtained by drying is separated from the support to form a single antifogging film B) a method of forming a coating film directly on the surface of the article to which antifogging properties are to be applied, and drying it.
  • the antifogging film since the antifogging film is in an independent state alone, it can be used at any place by the user.
  • peeling is facilitated by apply
  • the antifogging film after peeling can also laminate
  • the support is not limited, and may be, for example, glass, ceramics, metal, plastics or the like. Further, the surface shape of the support is also not limited, and may be, for example, any of a flat surface, a curved surface, and an uneven surface (rough surface).
  • the antifogging film When the antifogging film is applied to the surface of the article, it may be attached using an adhesive or a pressure-sensitive adhesive, if necessary.
  • the antifogging film can be directly applied to the article, so that the manufacturing process can be simplified.
  • the article targeted by the method of the above b) is not particularly limited, and can be applied to any article for which antifogging properties are required.
  • the surface of the article may be treated with an appropriate adhesive or pressure-sensitive adhesive, or a primer, in order to enhance the adhesion between the article surface and the antifogging film.
  • the coating method is not limited, and various coating methods such as brush, roller, spray, blade, dipping and the like can be adopted.
  • an antifogging film can be obtained by drying the coating film (undried coating film) formed by methods, such as said a) and b).
  • drying may be either heat drying or natural drying, but in particular, it is preferable to relatively slowly dry at around room temperature (especially 5 to 35 ° C.).
  • room temperature especially 5 to 35 ° C.
  • an acrylic block copolymer to self-organize phase separation
  • it is possible to obtain an antifogging film having the above-mentioned spherical structure, cylindrical structure, alternate lamella structure and the like.
  • the heat treatment such as thermal annealing is unnecessary in the formation of the antifogging film, it can also contribute to the simplification of the manufacturing apparatus and the like.
  • an antifogging product which formed such an antifogging film on the article surface, it is the same as that of the conventional antifogging product, for example, a) window glass of a building structure, a car, etc. b) mirror surface of bathroom and vanity C) Lenses or lens covers such as glasses, goggles and face masks d) various illuminations, lighting covers such as headlights d) covers such as display devices and monitors e) glass surfaces such as a cold storage showcase or the like A transparent resin surface etc. are mentioned.
  • Example 1 (1) Synthesis of block copolymer In a two-necked flask, cyclohexyl acrylate (CHA) (7.71 g, 50 mmol,) as the first component monomer, 2-cyano-2-propyldodecyl trithiocarbonate (0.35 g, as the RAFT reagent) 1.00 mmol), dimethyl-2,2'-azobis (2-methylpropionic acid) (0.12 g, 0.50 mmol) as a polymerization initiator, ethyl acetate (7.71 g) as a solvent, and nitrogen bubbling the reaction mixture The mixture was stirred for 30 minutes while stirring. The reaction mixture was warmed to 80 ° C. and stirred at 80 ° C.
  • CHA cyclohexyl acrylate
  • 2-cyano-2-propyldodecyl trithiocarbonate (0.35 g, as the RAFT reagent
  • HeA normal hexyl acrylate
  • HeMA normal hexyl methacrylate
  • BuMA normal butyl methacrylate
  • MMA methyl methacrylate
  • IBXA isoboronyl acrylate
  • Test Example 1 The antifogging properties of the copolymer films obtained in the examples and comparative examples were evaluated.
  • the method for evaluating the antifogging property is as follows.
  • the antifogging coating test piece is disposed at a position 1 cm high from the water surface of the 40 ° C. warm water bath in the air (room temperature 20 ° C.) so that the copolymer film faces downward.
  • the copolymer film was exposed to steam from a hot water bath. After 2 minutes, it was visually confirmed whether or not haze was formed on the copolymer film.
  • the case where cloudiness does not occur on the copolymer film surface is described as "o”
  • the case where cloudiness occurs on the copolymer film surface is described as "x”.
  • Table 1 The results are shown in Table 1.
  • SP value (unit: [cal / cm ⁇ 2 >] ⁇ 1/2 >) of the polymer which comprises each block is as follows.
  • the block copolymer film consisting of CHA and DMAA in Examples 1 to 3 can obtain excellent antifogging properties.
  • FIG. 1 it can be seen that, with the antifogging film of the present invention, a film capable of microphase separation (self-assembly) can be prepared, and high antifogging durability can be expected. It was confirmed that the copolymer films of Examples 4 to 7 exhibited good antifogging properties other than the combination of CHA and DMAA.
  • Tg glass transition point
  • the copolymer films of Comparative Examples 1 to 3 are block copolymer films using components having a high Tg other than CHA, so that the desired antifogging properties can not be obtained. This is considered to be because the high Tg causes the hydrophobicity and the crystallinity to be increased, and as a result, the water absorption is inhibited, so that the antifogging property is lowered.
  • a block copolymer film having a microphase separation structure can be produced, good antifogging properties can be obtained, and as a result, it can be used as an antifogging film applied to various articles.

Abstract

Le problème décrit par la présente invention est de fournir : un film antibuée capable de présenter de manière durable d'excellentes propriétés antibuée ; et un copolymère acrylique séquencé pour la fabrication de celui-ci. La solution selon l'invention consiste en : un copolymère acrylique séquencé qui comprend des motifs répétés hydrophiles et hydrophobes, et qui est caractérisé en ce que (1) le paramètre de solubilité d'un polymère constituant un motif hydrophobe est inférieur à 10 [cal/cm2]1/2 et le paramètre de solubilité d'un polymère constituant un motif hydrophile est égal ou supérieur à 10 [cal/cm2]1/2, et (2) le motif hydrophobe est un polymère présentant une température de transition vitreuse égale ou inférieure à 50 °C ; et un film antibuée contenant le copolymère acrylique séquencé.
PCT/JP2018/047493 2017-12-27 2018-12-25 Copolymère acrylique séquencé et film antibuée en contenant WO2019131597A1 (fr)

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