WO2019124089A1 - Agent de revêtement destiné à des films de dépôt en phase vapeur, film barrière aux gaz et matériau d'emballage - Google Patents

Agent de revêtement destiné à des films de dépôt en phase vapeur, film barrière aux gaz et matériau d'emballage Download PDF

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Publication number
WO2019124089A1
WO2019124089A1 PCT/JP2018/044880 JP2018044880W WO2019124089A1 WO 2019124089 A1 WO2019124089 A1 WO 2019124089A1 JP 2018044880 W JP2018044880 W JP 2018044880W WO 2019124089 A1 WO2019124089 A1 WO 2019124089A1
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Prior art keywords
film
coating agent
acid
vapor deposition
polyester
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PCT/JP2018/044880
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English (en)
Japanese (ja)
Inventor
知樹 土肥
加賀谷　浩之
常行 手島
明宏 近藤
武田　博之
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Dic株式会社
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Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2019519343A priority Critical patent/JP6551769B1/ja
Priority to CN201880079820.0A priority patent/CN111465664B/zh
Publication of WO2019124089A1 publication Critical patent/WO2019124089A1/fr

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    • 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
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; 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
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to a coating for a vapor deposition film, and a gas barrier film using the same.
  • Packaging materials such as food and beverages are often required to have gas barrier properties such as water vapor and oxygen barrier for the protection of the contents.
  • gas barrier properties such as water vapor and oxygen barrier for the protection of the contents.
  • a method of applying a gas barrier to a packaging material a method of applying a gas barrier coating to a stretched film or a method of providing a gas barrier resin on a layer in a multilayer film by coextrusion is widely used.
  • the vapor deposition method to apply is an excellent method that can easily impart a barrier function regardless of the type of gas.
  • the base film used in the vapor deposition method includes a stretched film and an unstretched film.
  • a stretched film and an unstretched film are used for a vapor deposited film provided with a metal deposited layer of aluminum or the like as a gas barrier layer.
  • the thickness of the vapor deposition layer is generally as thin as 10 to 50 nm, pinholes are likely to occur, and the gas barrier function may not be stable.
  • the base film is an unstretched film, the gas barrier function tends to be particularly unstable due to the fact that the film is easily stretched as compared with the stretched film and the gas barrier property of the film itself is poor.
  • overcoat techniques for transparent deposited layers for example, in Patent Document 1 and Patent Document 2, an inorganic oxide layer, a so-called transparent deposited layer, a water-soluble polymer and (a) one or more metal alkoxides, (b A gas barrier coating layer formed by applying a gas barrier coating solution containing as a main component an aqueous solution containing at least one or more of hydrolysates of one or more metal alkoxides or (c) tin chloride, or a water / alcohol mixed solution A transparent gas barrier laminate is described.
  • the water-soluble polymer has poor coating drying properties and contains a sol-gel process in which it is difficult to control the reaction, the reaction management and reuse of the overcoat liquid are difficult, and the coating method has a complicated problem.
  • a resin composition A comprising at least two base layers and comprising polypropylene, and a mixture of a cyclic polyolefin polymer and a polyolefin comprising a copolymer of norbornene and ethylene
  • the non-stretched aluminum vapor deposition film which provided the aluminum vapor deposition layer on this base material layer which consists of a structure which laminated
  • this method stability such as barrier property is imparted by vapor deposition on a film substrate containing a cyclic polyolefin-based polymer having heat resistance and dimensional stability higher than that of polypropylene alone.
  • this method uses a film having a two-layer structure as a base film, and has a problem that the manufacturing method is complicated and the cost is increased.
  • the applicants of the present invention have, as a multilayer film excellent in gas barrier properties, a polyester polyol having two or more hydroxyl groups, for example, a polyvalent carboxylic acid component containing at least one ortho-oriented aromatic dicarboxylic acid or its anhydride. It has been found that a gas barrier adhesive layer comprising a polyisocyanate having two or more isocyanate groups, and a gas barrier multilayer film having an aluminum deposited layer or a layer containing an aluminum foil is excellent in gas barrier properties. (See, for example, Patent Document 4).
  • the adhesive used for the gas barrier film is a reactive two-component adhesive, it has been necessary to immediately coat the deposited film and laminate it with the second base after mixing as the adhesive. That is, for the purpose of protecting the deposited layer of the deposited film itself, for example, a second substrate is required to protect the deposited layer of the deposited film, and a laminating apparatus is required to apply the adhesive. Again, the process is complicated.
  • JP 2012-101505 A JP 2012-250470 A JP 2011-224921 A JP, 2013-147014, A
  • the problem to be solved by the present invention is that the coating on the surface of the deposited film is easy, and the obtained coating film is excellent in adhesion to the deposited film, and the deposited film after coating has excellent blocking resistance and gas barrier properties.
  • An object of the present invention is to provide an excellent coating agent for deposited film.
  • the present inventors have an ester skeleton derived from polyester (A3) which is a polycondensate of polyvalent carboxylic acid component (A1) and polyvalent alcohol component (A2), and the polyvalent carboxylic acid component (A1)
  • the present inventors are polyhydric alcohol components containing 50 to 100 mol% of a polyvalent carboxylic acid component (B1) containing at least one of ortho-oriented aromatic dicarboxylic acids or their anhydrides as a polyester component It finds that it is excellent in blocking resistance by using polyester (B) obtained by polycondensing (B2), and also when it is a case where it laminates using a general-purpose adhesive, It has been found that a coating agent having excellent adhesion without peeling between vapor deposited films can be obtained.
  • the present invention is a coating agent for deposited film, comprising a polyisocyanate compound (A) and a polyester (B),
  • the polyisocyanate compound (A) has an ester skeleton derived from polyester (A3) which is a polycondensate of polyvalent carboxylic acid component (A1) and polyvalent alcohol component (A2), and the polyvalent carboxylic acid A polyisocyanate compound (A) containing 10 to 70 mol% of at least one ortho-oriented aromatic dicarboxylic acid or an acid anhydride thereof with respect to the total amount of the component (A1)
  • the polyester (B) is a polycondensate of a polyvalent carboxylic acid component (B1) containing at least one of an ortho-oriented aromatic dicarboxylic acid or an anhydride thereof and a polyvalent alcohol component (B2), and the polyvalent alcohol component (B2)
  • a coating agent for deposited film is provided, which contains 50 to 100 mol% of glycerol based on the total amount.
  • the present invention also provides a gas barrier film obtained by coating a vapor deposition film with the coating agent described above.
  • the present invention also provides a packaging material using the gas barrier film described above.
  • the coating agent for a vapor deposition film of the present invention can be diluted with a solvent and can be easily applied to the surface of the vapor deposition film. Moreover, since a coating film is excellent in the adhesiveness to a vapor deposition film, the film which coated the coating agent for vapor deposition films of this invention on the vapor deposition film is excellent not only in gas barrier property but in lamination strength. Moreover, since the film which coated the coating agent for vapor deposition films of this invention to the vapor deposition film uses a specific polyester, it is excellent also in blocking resistance.
  • the gas barrier film obtained by coating the metallized film with the coating agent for a vapor deposition film of the present invention has excellent gas barrier properties without using a multi-layered laminate with an adhesive or the like, so a barrier film useful particularly for food packaging. Can be provided at low cost.
  • the present invention is a coating agent for a deposited film comprising a polyisocyanate compound (A) and a polyester (B).
  • the polyester (B) has a carboxyl group or a hydroxyl group at the end, and reacts with the isocyanate group of the polyisocyanate compound (A).
  • the polyisocyanate compound (A) used in the present invention has an ester skeleton derived from a polyester (A3) which is a polycondensate obtained by polycondensing a polyvalent carboxylic acid component (A1) and a polyhydric alcohol component (A2). And has an isocyanate group at the end. Since the polyester (A3) has a hydroxyl group or a carboxyl group at the end, introduction of the terminal isocyanate group is carried out by reacting the terminal hydroxy group or carboxyl group of the polyester (A3) with a polyisocyanate compound.
  • polyisocyanate compound examples include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate and hexamethylene diisocyanate.
  • a polyisocyanate compound containing an aromatic ring in part of the skeleton is preferable because the gas barrier function can be further improved.
  • the number average molecular weight of the polyester (A3) is preferably 300 to 2,000.
  • the number average molecular weight or weight average molecular weight is detected by gel permeation chromatography using a GPC column LF-804 (manufactured by Showa Denko) by a differential refractive index detector (Waters 2414 manufactured by Waters). It measured from the retention time.
  • the polyester (A3) is used by polycondensing a polyhydric carboxylic acid component (A1) and a polyhydric alcohol component (A2).
  • the polyvalent carboxylic acid component (A1) contains 10 to 70 mol% of at least one ortho-orientation aromatic dicarboxylic acid or an acid anhydride thereof with respect to the total amount of the polyvalent carboxylic acid component (A1) It is a feature.
  • An aromatic polyvalent carboxylic acid or an acid anhydride thereof in which the carboxylic acid is substituted at the ortho position (hereinafter referred to as “an aromatic polyvalent carboxylic acid or an acid anhydride thereof in which the carboxylic acid is substituted at an ortho position”
  • Component (C1) may be referred to as “orthophthalic acid or an anhydride thereof, naphthalene 2,3-dicarboxylic acid or an anhydride thereof, naphthalene 1,2-dicarboxylic acid or an anhydride thereof, anthraquinone 2,3- Examples thereof include dicarboxylic acids or their anhydrides, and 2,3-anthracene carboxylic acids or their anhydrides.
  • These compounds may have a substituent at any carbon atom of the aromatic ring.
  • substituents include chloro group, bromo group, methyl group, ethyl group, i-propyl group, hydroxyl group, methoxy group, ethoxy group, ethoxy group, phenoxy group, methylthio group, phenylthio group, cyano group, nitro group, amino group, Examples thereof include phthalimido group, carboxyl group, carbamoyl group, N-ethylcarbamoyl group, phenyl group and naphthyl group.
  • polyvalent carboxylic acid components may be copolymerized as long as the effects of the present invention are not impaired.
  • aliphatic polyvalent carboxylic acids succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc.
  • unsaturated bond-containing polyvalent carboxylic acids maleic anhydride, maleic acid, Fumaric acid etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc.
  • p- Dorokishi benzoic acid can be used in p-(2-hydroxyethoxy) benzoic acid and alone or in mixture of two or more polybasic acids such as ester-forming derivatives of these dihydroxy carboxylic acids.
  • succinic acid, adipic acid, 1,3-cyclopentanedicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalic acid and diphenic acid are preferable from the viewpoint of organic solvent solubility and gas barrier property.
  • acid component (C2) other carboxylic acid or acid anhydride
  • the polyhydric alcohol component (A2) contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol and neopentyl glycol. Among them, it is most preferable to use ethylene glycol as the main component, since it is presumed that the oxygen permeation is difficult as the molecular chain is not excessively flexible as the number of carbon atoms between oxygen atoms decreases.
  • polyhydric-alcohol component (A2) in this invention, you may copolymerize another polyhydric-alcohol component in the range which does not impair the effect of this invention besides this.
  • the polycondensation reaction of the polyvalent carboxylic acid component (A1) with the polyvalent alcohol component (A2) can be carried out by a known and commonly used method.
  • the polyester polyol of the central skeleton of the polyisocyanate compound (A3) preferably has a hydroxyl value of 50 to 400 mg KOH / g and an acid value of 2 mg KOH / g or less.
  • the hydroxyl value can be measured by the hydroxyl value measurement method described in JIS-K 0070, and the acid value can be measured by the acid value measurement method described in JIS-K 0070.
  • the hydroxyl value is less than 50 mg KOH / g, the molecular weight is too large, so the viscosity may be high, and good coating suitability may not be obtained. Conversely, if the hydroxyl value exceeds 400 mg KOH / g, the molecular weight is small. Since it is too large, the crosslink density of the cured coating film may be too high, and good adhesive strength may not be obtained.
  • the isocyanate used in the present invention may be either a low molecular weight compound or a high molecular weight compound, but a diisocyanate is preferred from the viewpoint of reaction control. Moreover, when an aromatic ring or an aliphatic ring is contained in part of the skeleton, it is more preferable from the viewpoint of the gas barrier improving function.
  • isocyanate having an aromatic ring metaxylylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate
  • isocyanate having an aliphatic ring hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, isophorone diisocyanate, norbornene diisocyanate
  • examples of other isocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, allophanate bodies of hexamethylene diisocyanate, biuret bodies and nurate bodies.
  • blocked isocyanate Moreover, as long as it is a polyisocyanate compound containing an aromatic ring and an aliphatic ring, it may be blocked isocyanate.
  • an isocyanate blocking agent for example, as long as it contains an aromatic group, phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, phenols such as chlorophenol, etc.
  • aromatic amines, imides, active methylene compounds such as acetylacetone, acetoacetate ester, malonic acid ethyl ester, mercaptans, imines, ureas, diaryl compounds, sodium bisulfite, etc. may be mentioned.
  • the blocked isocyanate is obtained by the addition reaction of the above-mentioned isocyanate compound and an isocyanate blocking agent by a conventionally known appropriate method.
  • the polyester (B) used in the present invention is produced by polycondensation of a polyvalent carboxylic acid component (B1) containing at least one of an ortho-oriented aromatic dicarboxylic acid or its anhydride with a polyhydric alcohol component (B2). Be done.
  • the molecular weight of the polyester (B) is not particularly limited as long as it can impart sufficient film toughness, coating suitability, and solvent solubility as a coating agent, but a number average molecular weight of 1,000 to 50,000 is preferable. More preferably, it is 1000 to 30000.
  • the functional group at the polyester end may have both an alcohol end and a carboxylic acid end, but in order to use an isocyanate-based curing agent in combination, it is preferable that the polyester polyol is mainly composed of an alcohol end.
  • Tg Glass transition temperature (Tg) of polyester (B)
  • the glass transition temperature (hereinafter sometimes referred to as Tg) of the polyester (B) used in the present invention is not particularly limited, but is preferably 15 ° C. or more.
  • Tg is 18 degreeC or more especially, More preferably, it is 25 degreeC or more.
  • Tg was measured by detecting the heat flow rate in a temperature range of ⁇ 50 ° C. to 100 ° C. using a differential scanning calorimeter (DSC 822e manufactured by METTLER TOLEDO).
  • the polyester (B) used in the present invention is used by polycondensing a polyvalent carboxylic acid component (B1) and a polyhydric alcohol component (B2).
  • the polyvalent carboxylic acid component (B1) is characterized in that it contains at least one of an ortho-oriented aromatic dicarboxylic acid or an anhydride thereof.
  • an ortho-oriented aromatic dicarboxylic acid or an anhydride thereof it is preferable to use an ortho-oriented aromatic dicarboxylic acid or an anhydride thereof, but in addition, the above-mentioned acid component (C2) can be used as long as the effects of the present invention are not impaired.
  • succinic acid 1,3-cyclopentanedicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalic acid and diphenic acid are preferable from the viewpoint of organic solvent solubility and gas barrier property.
  • the polyhydric alcohol component (B2) in the polyester (B) used in the present invention is characterized by containing glycerol and having a glycerol content of 50 to 100 mol% with respect to all the polyhydric alcohol components.
  • the glycerol content is 50 mol% or more, the molecular movement of the polyester resin is suppressed by the increase in the crosslinking point on the molecular structure, and the blocking function and the barrier function of the resin are improved.
  • the polyhydric alcohol component (B2) used in combination with glycerol is not particularly limited as long as it is possible to synthesize a polyester exhibiting the performance of gas barrier compensation, but ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexane dimethanol, and 1 It is preferable to contain a polyhydric alcohol component containing at least one selected from the group consisting of 3, 3-bishydroxyethylbenzene. Among them, it is most preferable to use ethylene glycol as the main component, since it is presumed that the oxygen permeation is difficult as the molecular chain is not excessively flexible as the number of carbon atoms between oxygen atoms decreases.
  • polyhydric alcohol component (B2) in addition to this, other polyhydric alcohol components may be copolymerized within the range not impairing the effects of the present invention.
  • diols 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene Glycol, tetraethylene glycol, dipropylene glycol and tripropylene glycol are tri- or higher alcohols, and trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1,2,4-butanetriol, Pentaerythritol, dipentaerythritol and the like can be mentioned.
  • polyesters which use tris (2-hydroxyethyl) isocyanurate in combination have good organic solvent solubility due to their branched structure and moderately high crosslink density, as well as barrier function. It is excellent and particularly preferably used.
  • the catalyst used for the reaction to obtain the polyester of the present invention includes tin-based catalysts such as monobutyl tin oxide, dibutyl tin oxide and the like, titanium-based catalysts such as tetra-isopropyl-titanate and tetra-butyl-titanate, tetra-butyl-zirconate and the like.
  • An acid catalyst such as a zirconia-based catalyst can be mentioned. It is preferable to use the titanium-based catalyst such as tetra-isopropyl-titanate or tetra-butyl-titanate having high activity to the ester reaction in combination with the above-mentioned zirconia catalyst.
  • the amount of the catalyst is 1 to 1000 ppm, preferably 10 to 100 ppm, based on the total mass of the reaction raw material used. If it is less than 1 ppm, it is difficult to obtain the effect as a catalyst, and if it exceeds 1000 ppm, there may occur a problem of inhibiting the urethanation reaction when using an isocyanate curing agent.
  • the coating agent for deposited film of the present invention contains the polyisocyanate compound (A) and the polyester (B), but the reaction of the polyisocyanate compound (A) It is preferable to blend so that the component and the hydroxyl group of polyester (B) are 0.5 / 1 to 5/1 (equivalent ratio), and from the viewpoint of the barrier function and blocking resistance, more preferably 1/1 to 5 It is 1.5 / 1. If the amount of the polyisocyanate component exceeds this range, excess blocking of the polyisocyanate component tends to result in poor blocking resistance. On the other hand, if the amount of polyester (B) is too large, the cured coating becomes hard and adhesion is good. There is a possibility that strength can not be obtained.
  • the coating agent of the present invention may appropriately use a solvent.
  • the solvent to be used is preferably a non-aqueous system from the viewpoint of compensating for the rapid drying property and the water vapor barrier function, and it is preferable that the organic solvent is the main component.
  • the solubility is high in the polyester which is the main component, and the residual solvent and the immediate drying property. From this viewpoint, an organic solvent having a boiling point of 100 ° C. or less is preferable.
  • Preferred organic solvents include ethyl acetate, propyl acetate and butyl acetate as ester solvents, acetone and 2-butanone as ketone solvents, tetrahydrofuran as ether solvents, and hexane as aliphatic solvents.
  • Examples of cyclohexane and aromatic solvents include toluene and the like.
  • the coating agent of the present invention may contain a plate-like inorganic compound.
  • a plate-like inorganic compound When a plate-like inorganic compound is used in the present invention, it has an effect of improving the winding suitability after coating and gas barrier properties by reducing the adhesiveness.
  • the barrier property is improved by the plate-like shape.
  • the charge between the layers of the plate-like inorganic compound does not directly affect the barrier property greatly, but the dispersibility with respect to the coating agent of the present invention is significantly inferior to the ionic inorganic compound or the swellable inorganic compound, and the addition amount
  • the coating suitability of the coating agent of the present invention becomes an issue due to the thickening and the thixotropy.
  • non-charging (non-ionic) or non-swelling property with respect to water even if the addition amount is increased, it becomes difficult to become thickened or thixotropic, and coating suitability can be secured.
  • Examples of the plate-like inorganic compound used in the present invention include, for example, water-containing silicates (phylosilicate minerals etc.), kaolinite-serpentine group clay minerals (halloysite, kaolinite, ende), for example.
  • the plate-like inorganic compounds are used singly or in combination of two or more.
  • the aspect ratio of the plate-like inorganic compound, the content in the coating agent, the particle diameter, and the particle size distribution are not particularly limited as long as the barrier improving function and the blocking resistance can be imparted.
  • a known dispersion method can be used.
  • ultrasonic homogenizers, high pressure homogenizers, paint conditioners, ball mills, roll mills, sand mills, sand grinders, dyno mills, disper mats, nano mills, SC mills, nanomizers, etc. can be mentioned, and still more preferably high shear force is generated
  • equipment that can be used include a Henschel mixer, a pressure kneader, a Banbury mixer, a planetary mixer, a double roll, a triple roll, and the like. One of these may be used alone, or two or more types of devices may be used in combination.
  • acid anhydride for the purpose of improving the acid resistance of the coating agent layer, known acid anhydrides may be used in combination as additives.
  • the acid anhydride for example, phthalic anhydride, succinic anhydride, hetic anhydride, hymic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydraphthalic anhydride, tetrabromophthalic acid Anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenotetracarboxylic acid anhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 5- (2 And 5, 5-oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, styrene-maleic anhydride copolymer and the like. It is preferable
  • the material which has a gas trapping function may be added further as needed.
  • the material having an oxygen scavenging function include hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, low molecular weight organic compounds that react with oxygen such as gallic acid, pyrogallol, cobalt, manganese, nickel, iron, Transition metal compounds, such as copper, etc. are mentioned.
  • the material having a water vapor capture function include materials such as silica gel, zeolite, activated carbon, calcium carbonate and the like. In addition to these, it is possible to add the capture component of the target gas to be blocked.
  • additives may be blended as long as the gas barrier auxiliary function is not impaired.
  • examples of the additive include inorganic fillers such as silica, alumina, aluminum flakes and glass flakes, and dispersants and stabilizers (antioxidants, heat stabilizers, UV absorbers, etc.) when using inorganic materials, and plastic Agents, antistatic agents, lubricants, antiblocking agents, colorants, leveling agents, slip improvers and the like.
  • the coating agent of the present invention is used to significantly improve the gas barrier properties of a vapor-deposited film. Therefore, various vapor deposition films are used as an object to which a coating agent is applied.
  • a film coated with the present material can be used as a high gas barrier film because it is more excellent in gas barrier properties than a general vapor deposition film.
  • Type of vapor deposition layer As a kind of vapor deposition layer of the vapor deposition film by which the coating agent used by this invention is apply
  • coated if gas-barrier property can be provided, it will not be specifically limited.
  • Metal deposition or metal oxide deposition widely used at present for packaging is suitably exemplified. Although various metals can be illustrated as metal vapor deposition, especially cheap and widely used aluminum is preferable.
  • the metal oxide aluminum oxide (AlOx) and silicon oxide (SiOx) are preferably exemplified as highly versatile materials. Other than this, a film in which various organic compounds and inorganic compounds are vapor-deposited, or a film in which plural kinds of materials are vapor-deposited may be used.
  • the vapor deposition method is not particularly limited, and examples thereof include a vacuum vapor deposition method which is a physical vapor deposition method and a CVD method which is a chemical vapor deposition method.
  • the thickness of the vapor deposition layer is not particularly limited as long as the vapor deposition layer can exhibit a certain gas barrier function even if it is a single vapor deposition layer, and if it can be made a high barrier film by providing a coating layer thereon. However, if the vapor deposition layer is too thin, the contribution of the vapor deposition layer to the gas barrier decreases, and even if the coating agent of the present invention is used, a sufficient gas barrier function can not be expressed. It is preferably 3 to 70 nm, more preferably 5 to 60 nm.
  • these vapor deposition films can be used as protection of vapor deposition, with or without overcoating or undercoating previously applied.
  • a vapor-deposited film having no coating layer is preferably used because the barrier enhancing function of the coating agent of the present invention can be sufficiently exhibited.
  • thermoplastic resin film can be appropriately selected according to the desired application.
  • PET polyethylene terephthalate
  • polystyrene film polyamide film
  • polyacrylonitrile film polyethylene film
  • LLDPE linear low density polyethylene film
  • HDPE high density polyethylene film
  • CPP unstretched
  • Polyolefin films such as polypropylene film, OPP: biaxially oriented polypropylene film
  • polyvinyl alcohol film ethylene-vinyl alcohol copolymer film
  • cycloolefin copolymer film and the like.
  • films can be preferably used with or without a stretching treatment. Films subjected to a stretching process have the advantages of dimensional stability, rigidity and easy coating operation and ease of use. In addition, the unstretched film conversely has poor dimensional stability, rigidity, and heat resistance of the substrate, and the vapor deposition layer has many defects, and in many cases the gas barrier is not stable. Therefore, using the coating agent of the present invention There is an advantage of strengthening the coating agent of the present invention.
  • a barrier film containing a gas barrier layer such as polyvinyl alcohol, ethylene / vinyl alcohol copolymer, vinylidene chloride or the like is used in combination to impart a higher barrier function. Also good.
  • the coating method of the coating agent of the present invention is not particularly limited as long as the deposition surface of the deposited film can be coated.
  • various coating methods such as call coat and gravure coat can be exemplified.
  • the film thickness to which the coating agent of the present invention is applied is not particularly limited.
  • the coating agent of the present invention enhances the reinforcing effect of the gas barrier by closing the deposition defects. Therefore, the coating film thickness does not need to be thick as long as the deposition defects can be closed, and if it is 0.1 ⁇ m or more, the barrier improvement effect can be obtained.
  • the preferable thickness range is a range of 0.2 ⁇ m to 5 ⁇ m, more preferably 0.3 to 3 ⁇ m, in view of the balance between the fact that coating defects are less likely to occur and the drying property.
  • composition using metal vapor deposition stretched film such as aluminum In the case of using a transparent vapor-deposited stretched film such as a coating agent / ink / vapor-deposited stretched film / laminated adhesive / sealant film 2) aluminum oxide of the present invention, Transparent vapor-deposited stretched film / coating agent of the present invention / ink / laminated adhesive / sealant film 3) Metallized non-stretched film such as aluminum, etc.
  • composition of stretched film / ink / laminated adhesive / coating of the present invention Agent / metal deposition unstretched film / coating / ink / metal deposition unstretched film 4) transparent vapor deposited unstretched film such as aluminum oxide etc. stretched film / ink / laminate adhesive / coating agent of the present invention / transparent deposition Unstretched film ⁇ Coating agent of the present invention / ink / transparent vapor deposited unstretched film
  • a high gas barrier film having two or less film layers and printed with an ink layer.
  • a metal or a transparent vapor deposited unstretched film is used, a single layer high barrier film can be provided.
  • Gases that can be blocked by the film for gas barrier using the coating agent of the present invention include oxygen, water vapor, carbon dioxide, inert gases such as nitrogen and argon, alcohol components such as methanol, ethanol and propanol, phenol, cresol, etc.
  • inert gases such as nitrogen and argon
  • alcohol components such as methanol, ethanol and propanol
  • phenol, cresol etc.
  • aroma components consisting of low molecular weight compounds such as soy sauce, sauce, miso, lemonon, menthol, methyl salicylate, coffee, cocoa shampoo, rinse, etc. can be exemplified.
  • the coating material of the present invention improves the barrier property of water vapor and oxygen of a vapor deposited film, and also has high laminating strength, and therefore, in addition to various packaging materials requiring laminating work, an adhesive for protective films for solar cells, for example.
  • coating agents for electronic materials such as coatings for water vapor barrier substrates for display devices, coatings for building materials, coatings for industrial materials, etc., suitably used for reinforcement of the gas barrier properties of water vapor and oxygen it can.
  • polyester polyol containing glycerol has a theoretical number average molecular weight calculated from the hydroxyl value and a number average molecular weight by the above measuring method greatly different from each other, so the actual number average molecular weight is described.
  • the number average molecular weight or weight average molecular weight is detected by gel permeation chromatography using a GPC column LF-804 (manufactured by Showa Denko) by a differential refractive index detector (Waters 2414 manufactured by Waters). It measured from the retention time.
  • Raw material monomer composition of polyester polyol (B) for Examples and Comparative Examples obtained in Production Examples 1 to 4 number average molecular weight of resin, glycerol content (mol%) with respect to all polyhydric alcohol components, polyvalent carboxylic acid
  • the content (mol%) of the ortho-oriented aromatic dicarboxylic acid or its anhydride with respect to all the components and the glass transition temperature (° C.) measured by the above-mentioned method are shown in Table 1.
  • the content (mol%) of the aromatic dicarboxylic acid or its anhydride is shown in Table 2, and the raw material monomer composition of the polyisocyanate compound for the examples and comparative examples obtained in Production Examples 11 to 16, NCO% (in the molecule)
  • the content (mol%) of the ortho-oriented aromatic dicarboxylic acid or the anhydride thereof with respect to the weight fraction of the isocyanate group) and the total component of the polyvalent carboxylic acid is shown in Tables 2 and 3.
  • XDI metaxylylene diisocyanate
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • the isocyanate used is as follows. ⁇ XDI: Mitsui Chemicals Co., Ltd. “Takenate 500” (nonvolatile component 100%) ⁇ TDI: Toron Co., Ltd. product "Corronate T-100” (non volatile matter 100%) -MDI: "Millionate MT" manufactured by Tosoh Corp. (nonvolatile component 100%) NCO%: It is an isocyanate group content with respect to a polyisocyanate compound (A), and is a measured value.
  • Example and Comparative Example The compounding ratio of the coating agent of the example and the comparative example and the film to be used are shown in Table 4.
  • the polyester (B) synthesized in the preparation example was added to 2-butanone and stirred with a stirrer at normal temperature. It was possible to prepare a solution in which all the polyesters were completely dissolved in the solvent. To the resulting solution was added the polyisocyanate compound (A) synthesized in the production example or a commercially available isocyanate compound, and the mixture was stirred with a stirrer at room temperature to prepare a uniform coating agent.
  • isocyanate compounds are as follows.
  • ⁇ D-110N Mitsui Chemicals Co., Ltd. “Takenate D-110N” (Meta-xylylene diisocyanate adduct, 75.0% of nonvolatile components, solvent ethyl acetate)
  • ⁇ KW-75 "DIC Dry KW-75” (manufactured by DIC Corporation) (Tolylene diisocyanate adduct, 75.0% nonvolatile component, solvent ethyl acetate)
  • T-1890 "VESTANATT-1890 / 100" (isophorone diisocyanate isocyanurate, 100% nonvolatile component) manufactured by EVONIC, diluted with ethyl acetate to prepare 70% nonvolatile component
  • Takenate 500 Mitsui Chemicals Co., Ltd. Made “Takenate 500” (Meta-xylylene diisocyanate, 100% non-volatile components)
  • the resulting coating agent is coated on the deposition side of the deposited film to a coating amount of 0.5 g / m 2 (solid content) using a bar coater # 2, and the solvent is applied by hot air at 80 ° C. with a dryer. After volatilization, the film was placed in a dryer set at 150 ° C. for 30 seconds to obtain a gas barrier film having a uniform coating layer. The following was used as a vapor deposition film which is a base material.
  • the gas barrier film was evaluated by measuring oxygen permeability, measuring water vapor permeability, measuring laminate strength, and blocking resistance (coating drying characteristics).
  • the gas barrier film used the film of (X) or (Y).
  • (Y) Laminated film using a gas barrier film The first substrate is compounded with Dick Dry LX-500 and KW-75 (both manufactured by DIC) at a compounding ratio of 10/1, and the nonvolatile content is 20%.
  • the adhesive obtained by blending ethyl acetate so as to become is coated to a coating amount of 2.0 g / m 2 (solid content) using a bar coater # 9, and the solvent is heated by a hot air at 80 ° C. with a dryer. Was allowed to evaporate.
  • dry lamination was performed with the second base material at a temperature of 40 ° C., a pressure of 0.4 MPa, and a laminating speed of 40 m / min to obtain a laminated film.
  • the laminated film was cured at 40 ° C./3 days to form a “laminated film”.
  • the gas barrier film obtained by the above-mentioned "method for producing a gas barrier film” was used as the first substrate or the second substrate.
  • the film abbreviations used are as follows.
  • Oxygen Permeability Measurement Method Using the gas barrier film of (X), the laminated film of (Y), and an untreated vapor-deposited film as a reference example, using an oxygen permeability measurement device OX-TRAN 2/21 MH manufactured by Mocon Corporation. It was measured in an atmosphere of 23 ° C. and 90% RH according to JIS-K7126 (isostatic pressure method). Here, RH indicates humidity.
  • the gas barrier film of (X), the laminated film of (Y), and an untreated vapor-deposited film as a reference example are cut in parallel with the coating direction to a width of 15 mm.
  • the tensile strength at the time of peeling between laminated films by the 180 degree peeling method is set as the lamination strength, using an STD-1225L table-top material tester made by And Day, setting the atmosphere temperature to 25 ° C. and the peeling speed to 300 mm / min. did.
  • the unit of laminate strength was N / 15 mm.
  • the coating agent contains 10 to 70 mol% of at least one ortho-orientation aromatic dicarboxylic acid or an acid anhydride thereof with respect to the total amount of the polyvalent carboxylic acid component (A1) shown in Examples 1 to 15.
  • the coating agent containing 50 to 100 mol% of glycerol relative to the total amount of the polyhydric alcohol component (B2) has low permeation of both oxygen and water vapor as compared to the vapor-deposited film to which the coating agent of the reference example is not applied. It exhibits excellent properties as a coating agent that shows the rate and improves the barrier function. Also, in any of the examples, the laminate film showed high laminate strength and showed excellent blocking resistance (coating film drying characteristic).
  • Comparative Examples 1 to 4 although a certain improvement in the barrier function was observed, the laminate film showed almost no laminate strength because it became a hard coating film derived from the chemical structure of the curing agent.
  • Comparative Examples 5 to 7 similarly having no essential structure of the present invention, strong adhesiveness remained after gas drying, which strongly suggested the possibility of problems such as blocking.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un agent de revêtement destiné à des films de dépôt en phase vapeur, qui contient : un composé polyisocyanate (A), qui possède un squelette ester dérivé d'un polyester (A3) qui est un produit de polycondensation d'un constituant d'acide carboxylique polyvalent (A1) et d'un constituant d'alcool polyhydrique (A2), et qui contient un acide dicarboxylique aromatique orthodirectionnel et/ou un anhydride d'acide de ce dernier dans une quantité de 10 à 70 % en moles par rapport à la quantité totale du constituant d'acide carboxylique polyvalent (A1) ; et un polyester (B), qui est un produit de polycondensation d'un constituant d'acide carboxylique polyvalent (B1) et d'un constituant d'alcool polyhydrique (B2), ledit constituant d'acide carboxylique polyvalent (B1) contenant un acide dicarboxylique aromatique orthodirectionnel et/ou un anhydride d'acide de ce dernier, et qui contient un glycérol en une quantité de 50 à 100 % en moles par rapport à la quantité totale du constituant d'alcool polyhydrique (B2). L'invention concerne également un film barrière aux gaz.
PCT/JP2018/044880 2017-12-20 2018-12-06 Agent de revêtement destiné à des films de dépôt en phase vapeur, film barrière aux gaz et matériau d'emballage WO2019124089A1 (fr)

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CN201880079820.0A CN111465664B (zh) 2017-12-20 2018-12-06 蒸镀膜用涂敷剂、阻气性膜和包装材料

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JP2021138856A (ja) * 2020-03-06 2021-09-16 東洋インキＳｃホールディングス株式会社 オーバーコート剤および印刷物
WO2023112687A1 (fr) * 2021-12-16 2023-06-22 Dic株式会社 Agent de revêtement durcissable à deux composants, corps stratifié et matériau d'emballage
WO2023181365A1 (fr) * 2022-03-25 2023-09-28 株式会社麗光 Film déposé en phase vapeur métallique

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JP2013129735A (ja) * 2011-12-21 2013-07-04 Dic Corp ガスバリアコーティング剤及びそれを用いたフィルム
JP2016011324A (ja) * 2014-06-27 2016-01-21 Dic株式会社 バリア材用ポリエステル樹脂組成物、及びバリアフィルム
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JP2021138856A (ja) * 2020-03-06 2021-09-16 東洋インキＳｃホールディングス株式会社 オーバーコート剤および印刷物
JP7472552B2 (ja) 2020-03-06 2024-04-23 ａｒｔｉｅｎｃｅ株式会社 オーバーコート剤および印刷物
WO2023112687A1 (fr) * 2021-12-16 2023-06-22 Dic株式会社 Agent de revêtement durcissable à deux composants, corps stratifié et matériau d'emballage
JP7375994B1 (ja) * 2021-12-16 2023-11-08 Dic株式会社 ２液硬化型コーティング剤、積層体、包装材
WO2023181365A1 (fr) * 2022-03-25 2023-09-28 株式会社麗光 Film déposé en phase vapeur métallique
JP7428455B1 (ja) 2022-03-25 2024-02-06 株式会社麗光 金属蒸着フィルム

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