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WO2014098069A1 - Composition de résine destinée à être utilisée comme adhésif formant une barrière contre la vapeur et stratifié - Google Patents

Composition de résine destinée à être utilisée comme adhésif formant une barrière contre la vapeur et stratifié Download PDF

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Publication number
WO2014098069A1
WO2014098069A1 PCT/JP2013/083727 JP2013083727W WO2014098069A1 WO 2014098069 A1 WO2014098069 A1 WO 2014098069A1 JP 2013083727 W JP2013083727 W JP 2013083727W WO 2014098069 A1 WO2014098069 A1 WO 2014098069A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
water vapor
film
acid
adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/083727
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English (en)
Japanese (ja)
Inventor
正憲 林
武田　博之
加賀谷　浩之
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2014524984A priority Critical patent/JP5761460B2/ja
Publication of WO2014098069A1 publication Critical patent/WO2014098069A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier

Definitions

  • the present invention relates to a resin composition capable of providing a film having excellent adhesive strength and water vapor barrier property, and a water vapor barrier film laminate obtained by curing the resin composition on the film.
  • Food packaging materials are required to have gas or water vapor barrier properties in order to protect their contents and extend their shelf life, and have been studied in many ways, including various plastic films, metals, glass-deposited films, metal foils, etc. Materials that have been laminated into composite films have been used. In order to satisfy the needs for the material having the gas barrier property, a transparent vapor-deposited film on which inorganic materials such as silica and alumina are vapor-deposited is used as the packaging material, but it is expensive and has poor bending resistance. There was a problem.
  • halogenated materials such as polyvinylidene chloride and cycloolefin copolymer systems were mainly used.
  • the adhesive used here is (1) adhesiveness to plastic film, aluminum vapor deposition film, alumina vapor deposition film, silica vapor deposition film, and aluminum foil, (2) initial adhesiveness to prevent tunneling, (3) adhesion High performance is required for the curing rate of the agent, (4) pot life, (5) content resistance, (6) boil, retort resistance and the like. More recently, various impurities derived from adhesives do not migrate to the contents and do not adversely affect the scent or taste. (7) Low odor properties have become important, but water vapor barrier properties The present condition is that the adhesive which has this is not known.
  • Patent Document 1 discloses a sheet excellent in water vapor barrier property, impact resistance, rigidity, and heat resistance containing a cyclic olefin in a resin composition, and a container formed of the sheet. ing.
  • Patent Document 2 describes a material that is a film or sheet containing a vinylidene chloride copolymer.
  • Patent Document 3 has an example using a maleimide compound having a condensed alicyclic structure, and describes that a water vapor barrier property can be imparted to the resulting sealant. .
  • Patent Document 4 discloses that polyurethane is developed as an adhesive for transparent inorganic vapor-deposited film and an anchor coating agent, polyester polyol is used as a polyurethane raw material, and tricyclodecane dimethanol is used as a glycol component. Are listed.
  • the problem to be solved by the present invention is to provide a resin composition capable of providing a film having excellent adhesive strength and water vapor barrier property, and a water vapor barrier film laminate obtained by curing the resin composition on the film. There is to do.
  • the present inventors are a resin composition for a water vapor barrier adhesive obtained by reacting a polyol and a curing agent, The above problems have been solved by providing a resin composition for a water vapor barrier adhesive, wherein the polyol or the curing agent has a tricycloalkane structure.
  • the present invention comprises the following items.
  • a resin composition for a water vapor barrier adhesive obtained by reacting a polyol and a curing agent, A resin composition for a water vapor barrier adhesive, which has a tricycloalkane structure in a polyol or a curing agent, 2.1.
  • the polyol is a polyester polyol obtained by reacting a tricycloalkane having a hydroxyl group with a polyvalent carboxylic acid or acid anhydride thereof and a polyhydric alcohol.
  • the curing agent is an isocyanate compound.
  • the isocyanate compound is a reaction product of metaxylene diisocyanate or metaxylene diisocyanate and a polyhydric alcohol having at least two hydroxyl groups in the molecule.
  • the isocyanate compound is a reaction product of a tris-cycloalkane having at least two or more hydroxyl groups in the molecule or a polyester polyol comprising tricycloalkane and isocyanate. ⁇ 4.
  • the tricycloalkane is tricyclodecane ⁇ 6.
  • a water vapor barrier film laminate obtained by curing the resin composition for water vapor barrier adhesive according to any one of the above on a film.
  • the present invention it is possible to provide a resin composition capable of providing a film having excellent adhesive strength and water vapor barrier properties, and a water vapor barrier film laminate obtained by curing the resin composition on the film.
  • the resin composition for water vapor barrier adhesive used in the present invention is a resin composition for water vapor barrier adhesive obtained by reacting a polyol and a curing agent, It is characterized by having a tricycloalkane structure in the polyol or the curing agent and having a tricycloalkane structure in the resin composition. Since the hydrophobicity of the resin composition by containing this structure is improved and the solubility of water vapor can be reduced, water vapor barrier properties are exhibited.
  • a resin composition that can be used as an adhesive having a water vapor barrier property is referred to as a resin composition for a water vapor barrier adhesive.
  • the polyol used in the present invention is not particularly limited as long as it reacts with a curing agent, but a tricycloalkane having a hydroxyl group and a polyvalent carboxylic acid or an acid anhydride thereof, or a tricycloalkane having a hydroxyl group and a polyvalent carboxylic acid. Or the polyol formed by making the acid anhydride and polyhydric alcohol react is mentioned.
  • Tricycloalkane having a hydroxyl group examples include known and commonly used tricycloalkanes having a hydroxyl group. Examples of the tricycloalkane include tricyclononane, tricyclononene, tricyclodecane, and tricycloalkane. Examples include cyclodecene, tricycloundecane, tricyclododecane, tricyclotetradecane, tricyclopentadecane, and tricyclohexadecane.
  • Polyvalent carboxylic acid Specifically, as the polyvalent carboxylic acid component used in the present invention, as the aliphatic polyvalent carboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and the like are used, and alicyclic polyvalent carboxylic acid.
  • 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like, and aromatic polyvalent carboxylic acids include orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic acid, 1,4 -Naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and the dicarboxylic acids Anhydrides or ester-forming derivatives; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) an Polybasic acids such as benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids can be used alone or in a mixture of two or more.
  • succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, acid anhydride of orthophthalic acid, and isophthalic acid are preferable, and orthophthalic acid and its acid anhydride are more preferable.
  • polyhydric alcohol component Specific examples of the polyhydric alcohol used in the present invention include aliphatic glycols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, and 3-methyl-1 , 5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyphenol , Hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, ethylene oxide De extension product, there can be mentioned hydrogenated alicyclic.
  • aliphatic glycols such as ethylene glyco
  • ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexane dimethanol are preferred, because it is estimated that the smaller the number of carbon atoms between oxygen atoms, the more difficult the molecular chain becomes excessively flexible. More preferred is ethylene glycol.
  • the polycondensation reaction between the polyvalent carboxylic acid and the polyhydric alcohol can be performed by a known and usual method.
  • polyester polyol examples include, but are not limited to, the following. (I); General formula (1)
  • A is a polyvalent carboxylic acid or its anhydride
  • B is a polyhydric alcohol having a tricyclodecane skeleton
  • a and B are bound by an ester group obtained by reaction with A and B.
  • N is an integer from 1 to 100.
  • A is a polyhydric carboxylic acid or its anhydride
  • B is a polyhydric alcohol having a tricyclodecane skeleton
  • C is a polyhydric alcohol other than a polyhydric alcohol having a tricyclodecane skeleton
  • a and C are bonded with an ester group obtained by reaction with A and B, A and C, and m and n are integers of 1 to 100.
  • A is a polyvalent carboxylic acid or its anhydride
  • B is a polyhydric alcohol having a tricyclodecane skeleton
  • C is a monovalent or polyhydric alcohol having a tricyclodecane skeleton
  • D is a polyhydric having a tricyclodecane skeleton.
  • A is a polyvalent carboxylic acid or anhydride thereof
  • B is a polyhydric alcohol having a tricyclodecane skeleton
  • C is a linear or branched alkyl group having 1 to 30 carbon atoms and having a hydroxyl group
  • B, A and C are bonded with an ester group obtained by reaction with A and B, A and C
  • n is an integer of 1 to 100.
  • A is a polyvalent carboxylic acid or its anhydride
  • B is a polyhydric alcohol other than a polyhydric alcohol having a tricyclodecane skeleton
  • C is a monovalent or polyhydric alcohol having a tricyclodecane skeleton
  • B, A and C are bonded with an ester group obtained by reaction with A and B, A and C, and n is an integer of 1 to 100.
  • the polyvalent carboxylic acid used in the present invention preferably contains a benzene ring, and particularly preferably includes orthophthalic acid and its anhydride.
  • the orthophthalic acid and its anhydride skeleton have an asymmetric structure. Therefore, it is presumed that the rotation of the molecular chain of the resulting polyester is suppressed, and it is presumed that this provides excellent gas barrier properties, particularly water vapor barrier properties. Further, it is presumed that the non-crystalline structure is exhibited due to this asymmetric structure, sufficient adhesion to the base material is imparted, and excellent adhesion and gas barrier properties, particularly water vapor barrier properties. Furthermore, when used as a dry laminate adhesive, the solvent solubility, which is essential, is also high, so that it has excellent handling characteristics.
  • the polyvalent carboxylic acid containing the cyclohexane skeleton which hydrogenated the benzene ring is used, since hydrophobicity improves and the solubility of water vapor
  • Polyvalent carboxylic acid and other components When synthesizing a polyester polyol having three or more hydroxyl groups, when a branched structure is introduced by a polyvalent carboxylic acid component, it is necessary to have at least part of a trivalent or higher carboxylic acid. Examples of these compounds include trimellitic acid and its acid anhydride, pyromellitic acid and its acid anhydride, etc. In order to prevent gelation during synthesis, trivalent or higher polyvalent carboxylic acids include three. Divalent carboxylic acids are preferred.
  • the polyester polyol of the present invention may be copolymerized with other polyvalent carboxylic acid components as long as the effects of the present invention are not impaired.
  • the aliphatic polyvalent carboxylic acid succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc.
  • the unsaturated bond-containing polyvalent carboxylic acid maleic anhydride, maleic acid, Fumaric acid, etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc.
  • polyhydric alcohol and other ingredients When synthesizing a polyester polyol having three or more hydroxyl groups, when a branched structure is introduced by a polyhydric alcohol component, it is necessary to have at least part of a trihydric or higher polyhydric alcohol.
  • these compounds include glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1,2,4-butanetriol, pentaerythritol, and dipentaerythritol.
  • trihydric alcohol is preferable as the trihydric or higher polyhydric alcohol.
  • aliphatic diols include 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, Triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyphenols, hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, and their ethylene oxides
  • An elongated product and a hydrogenated alicyclic group can be exemplified.
  • the synthesis of the polyester polyol can be performed using a known and commonly used method (for details, refer to Examples).
  • the polyester polyol preferably has a hydroxyl value of 20 to 250 and an acid value of 20 to 200.
  • the hydroxyl value can be measured by the hydroxyl value measuring method described in JIS-K0070, and the acid value can be measured by the acid value measuring method described in JIS-K0070.
  • the hydroxyl value is smaller than 20 mgKOH / g, the molecular weight is too large, the viscosity becomes high, and good coating suitability cannot be obtained.
  • the hydroxyl value exceeds 250 mgKOH / g, the molecular weight becomes too small, so that the crosslinking density of the cured coating film becomes too high, and good adhesive strength cannot be obtained.
  • steam barrier adhesives in this application is computable as follows. That is,
  • TMW Tricycloalkane molecular weight n: Degree of polymerization (in the case of containing a tricycloalkane structure at the terminal, n + 1)
  • NMW repeating unit molecular weight
  • EMW terminal monomer molecular weight
  • W main agent or curing agent blending amount containing tricycloalkane structure
  • AW main agent + curing agent blending amount.
  • the ratio of the tricycloalkane structure contained in the resin composition for a water vapor barrier adhesive of the present invention is preferably 10% by mass to 50% by mass.
  • the curing agent used in the present invention is not particularly limited as long as it can react with the hydroxyl group of the polyol, and known curing agents such as diisocyanate compounds, polyisocyanate compounds, and epoxy compounds can be used. Especially, it is preferable to use a polyisocyanate compound from a viewpoint of adhesiveness or retort resistance.
  • Polyisocyanate compounds include aromatic and aliphatic diisocyanates and trivalent or higher polyisocyanate compounds, which may be either low molecular compounds or high molecular compounds.
  • the isocyanate compound may be a blocked isocyanate.
  • the isocyanate blocking agent for example, phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime oximes, methanol, Alcohols such as ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; Examples include lactams such as caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propylolactam, and other aromatic amines, imides, acetylacetate.
  • the blocked isocyanate can be obtained by subjecting the above isocyanate compound and the isocyanate blocking agent to an addition reaction by a known and appropriate method.
  • metaxylene diisocyanate or a reaction product of metaxylene diisocyanate and a polyhydric alcohol having at least two hydroxyl groups in the molecule is preferable.
  • the glass transition temperature of the cured coating film of the polyol of the present invention and the curing agent is preferably in the range of ⁇ 30 ° C. to 80 ° C. More preferably, it is 0 ° C to 70 ° C. More preferably, it is 25 ° C to 70 ° C.
  • the glass transition temperature is higher than 80 ° C., the flexibility of the cured coating film near room temperature becomes low, and thus the adhesiveness to the substrate may be deteriorated due to poor adhesion to the substrate.
  • Epoxy compounds include bisphenol A diglycidyl ether and oligomers thereof, hydrogenated bisphenol A diglycidyl ether and oligomers thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid diglyceride.
  • Glycidyl ester tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 , 4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol Cole diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl
  • a general-purpose known epoxy curing accelerator may be appropriately added for the purpose of accelerating curing as long as the barrier property which is the object of the present invention is not impaired.
  • the curing agent is preferably a polyisocyanate compound having an aromatic ring. If the polyisocyanate compound includes the metaxylene skeleton, the barrier is not only caused by hydrogen bonding of the urethane group but also by ⁇ - ⁇ stacking of aromatic rings. It is preferable because the property can be improved.
  • Examples of the polyisocyanate compound containing the meta-xylene skeleton include a trimer of xylylene diisocyanate, a burette synthesized by reaction with an amine, and an adduct obtained by reacting with an alcohol.
  • the adduct body is more preferable because the solubility of the polyisocyanate compound in the organic solvent used for the dry laminate adhesive is easily obtained as compared with the body.
  • an adduct obtained by reacting with an alcohol appropriately selected from the above low molecular active hydrogen compounds can be used. Among them, addition of ethylene oxide of trimethylolpropane, glycerol, triethanolamine, metaxylenediamine, etc. Adduct bodies with objects are particularly preferred.
  • the resin composition and the curing agent are such that the ratio of the resin composition to the curing agent is such that the hydroxyl group of the resin composition and the reaction component of the curing agent are 1 / 0.5 to 1/10 (equivalent ratio). It is preferably blended in, more preferably 1/1 to 1/5. If the curing agent component is excessive beyond this range, the excess curing agent component may be left out and bleed out from the adhesive layer after bonding. On the other hand, if the curing agent component is insufficient, the adhesive strength is insufficient. There is a fear.
  • the above-mentioned curing agent can be used in combination with a known curing agent or accelerator selected according to the type.
  • the adhesion promoter include silane coupling agents such as hydrolyzable alkoxysilane compounds, titanate coupling agents, aluminum coupling agents, and epoxy resins. Silane coupling agents and titanate coupling agents are also preferred in terms of improving the adhesive to various film materials.
  • the adhesive of the present invention may contain various additives as long as the adhesive strength and the barrier property are not impaired.
  • additives include inorganic fillers such as silica, alumina, aluminum flakes, and glass flakes, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, antistatic agents, lubricants, and antiblocking agents. Examples include agents, colorants, fillers, crystal nucleating agents and the like.
  • Plate-like inorganic compound In the resin composition for adhesives of this invention, you may contain a plate-shaped inorganic compound.
  • the plate-like inorganic compound used in the present invention has an effect of improving the laminate strength and barrier properties of an adhesive obtained by curing a resin composition for an adhesive.
  • the plate-like inorganic compound used in the present invention has a feature that the laminate strength and barrier properties are improved by the plate-like shape.
  • the charge between the layers of the plate-like inorganic compound does not greatly affect the barrier property directly, but the dispersibility to the resin composition is greatly inferior with the ionic inorganic compound or the swellable inorganic compound with respect to water, and the amount added is increased. As a result, the resin composition becomes thicker and thixotropic.
  • the addition amount is increased, it is difficult to become thickened or thixotropic, so that the coating suitability can be secured.
  • Examples of the plate-like inorganic compound used in the present invention include, for example, hydrous silicate (phyllosilicate mineral etc.), kaolinite-serpentine clay mineral (halloysite, kaolinite, ende Light, dickite, nacrite, etc., antigolite, chrysotile, etc.), pyrophyllite-talc group (pyrophyllite, talc, kellorai, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, Sauconite, stevensite, etc.), vermiculite group clay minerals (vermiculite etc.), mica or mica group clay minerals (muscovite, phlogopite etc.
  • hydrous silicate phyllosilicate mineral etc.
  • kaolinite-serpentine clay mineral halloysite, kaolinite, ende Light, dickite, nacrite, etc.,
  • mica margarite, tetrasilic mica, teniolite, etc.
  • chlorite group kukeite, sudite
  • Clinocroix Clinocroix, sha Site Nimaito etc.
  • hydrotalcite tabular barium sulfate
  • boehmite boehmite
  • aluminum polyphosphate aluminum polyphosphate and the like.
  • These minerals may be natural clay minerals or synthetic clay minerals.
  • An inorganic layered compound is used individually or in combination of 2 or more types.
  • the plate-like inorganic compound used in the present invention is preferably nonionic without intercalation.
  • Examples of the plate-like inorganic compound used in the present invention include kaolinite-serpentine clay minerals (such as halloysite, kaolinite, enderite, dickite, nacrite, antigolite, chrysotile, etc.), pyrophyllite, and the like.
  • kaolinite-serpentine clay minerals such as halloysite, kaolinite, enderite, dickite, nacrite, antigolite, chrysotile, etc.
  • pyrophyllite and the like.
  • the talc family pyrophyllite, talc, kerolai, etc.
  • the plate-like inorganic compound used in the present invention is preferably non-swellable with respect to water.
  • Examples of the plate-like inorganic compound used in the present invention include kaolinite-serpentine clay minerals (such as halloysite, kaolinite, enderite, dickite, nacrite, antigolite, chrysotile, etc.), pyrophyllite, and the like.
  • kaolinite-serpentine clay minerals such as halloysite, kaolinite, enderite, dickite, nacrite, antigolite, chrysotile, etc.
  • pyrophyllite and the like.
  • -Talc pyrophyllite, talc, kerolai, etc.
  • mica or mica clay minerals mica, muscovite, phlogopite, etc.
  • margarite tetrasilic mica
  • teniolite etc.
  • chlorite kukeite, sudite, (Clinochlor, chamosite, nimite, etc.)
  • hydrotalcite plate-like barium sulfate and the like.
  • the average particle size in the present invention means a particle size having the highest appearance frequency when the particle size distribution of a certain plate-like inorganic compound is measured with a light scattering type measuring device.
  • the average particle diameter of the plate-like inorganic compound used in the present invention is not particularly limited, but is preferably 0.1 ⁇ m or more, and more preferably 1 ⁇ m or more. If the average particle size is 0.1 ⁇ m or less, the length of the long side is short, so that there are problems that the detour path of the molecule does not become long and the barrier ability is difficult to improve and the adhesive force is difficult to improve.
  • the side with a large average particle diameter is not particularly limited. When defects such as streaks occur on the coated surface by containing a large plate-like inorganic compound by the coating method, a material having an average particle diameter of 100 ⁇ m or less, more preferably 20 ⁇ m or less is preferably used.
  • the aspect ratio of the plate-like inorganic compound used in the present invention is preferably higher in order to improve the barrier ability due to the gas maze effect. Specifically, it is preferably 3 or more, more preferably 10 or more, and most preferably 40 or more.
  • a known dispersion method can be used as a method for dispersing the inorganic compound used in the present invention in a resin composition or a resin composition for a water vapor barrier adhesive.
  • a known dispersion method can be used.
  • an ultrasonic homogenizer, a high-pressure homogenizer, a paint conditioner, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a disperse mat, a nano mill, an SC mill, a nanomizer, and the like can be mentioned, and even more preferably, a high shear force is generated.
  • equipment that can be used include Henschel mixer, pressure kneader, Banbury mixer, planetary mixer, two-roll, three-roll. One of these may be used alone, or two or more devices may be used in combination.
  • the adhesive and film laminate of the present invention can also block gases other than water vapor.
  • gases other than water vapor examples include oxygen, alcohol, inert gas, and volatile organic substances (fragrance).
  • the alcohol targeted for blocking by the adhesive and multilayer film of the present invention is a material generally classified as an alcohol having a structure in which a hydroxyl group is bonded to an alkyl chain in at least one place. If there is no particular limitation. Moreover, monohydric alcohol or polyhydric alcohol can be used. Examples of the monohydric alcohol include methanol, ethanol, 1-propanol, 2-propanol, butanol, pentanol, neopentyl glycol, hexanol, benzyl alcohol, allyl alcohol, and cyclohexanol.
  • polyhydric alcohol examples include ethylene glycol, propanediol, butanediol, glycerin, and trimethylpropane.
  • polyhydric alcohol examples include ethylene glycol, propanediol, butanediol, glycerin, and trimethylpropane.
  • aminoalcohols such as N, N-diethylethanolamine, N, N-dimethylethanolamine, N-methyldiethanolamine and N-ethylethanolamine
  • alcohol compounds containing ether groups such as diethylene glycol and triethylene glycol Etc.
  • a material that is a gas to a liquid in a normal temperature region is preferable because of high effectiveness of the present invention.
  • the inert gas that is intended to be blocked by the adhesive and multilayer film of the present invention is inert to foods and is unlikely to cause a general chemical change. It is a gas useful for maintaining the flavor of food, maintaining its contents, and preventing oxidation by functions such as preventing contact.
  • nitrogen and carbon dioxide helium, neon, argon, krypton, xenon, and radon rare gases can be exemplified. Of these, nitrogen, argon, and carbon dioxide are widely used as the inert gas.
  • Volatile organic substances (fragrances) targeted for blocking by the adhesive and multilayer film of the present invention are cocoa, soy sauce, sauce, miso, coffee, lemonene, methyl salicylate, menthol, cheese, flavors, shampoo, rinse Sanitary field containing scent components such as detergents, softeners, soaps, pet foods, insect repellents, fragrances, hair dyes, perfumes, agricultural chemicals and the like.
  • the adhesive and multilayer film of the present invention can block gas, adsorbents such as activated carbon and zeolite, deodorants, water purifier cartridges, rice grains, instant noodles, mineral water, somen, cotton, etc. It is also suitably used for applications where it is desired to prevent the entry of fragrance from the outside and for applications where it is desired to prevent leakage of the fragrance to the outside.
  • adsorbents such as activated carbon and zeolite, deodorants, water purifier cartridges, rice grains, instant noodles, mineral water, somen, cotton, etc. It is also suitably used for applications where it is desired to prevent the entry of fragrance from the outside and for applications where it is desired to prevent leakage of the fragrance to the outside.
  • the adhesive of the present invention may be either a solvent type or a solventless type.
  • the solvent may be used as a reaction medium during the production of the polyester polyol and the curing agent. Furthermore, it is used as a diluent during painting.
  • Solvents that can be used include, for example, esters such as ethyl acetate, butyl acetate and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran and dioxane, and aromatic hydrocarbons such as toluene and xylene.
  • Halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide and the like. Of these, it is usually preferable to use ethyl acetate or methyl ethyl ketone.
  • the adhesive of the present invention can be used by being applied to a substrate film or the like.
  • the coating method is not particularly limited and may be performed by a known method.
  • a solvent type whose viscosity can be adjusted
  • it is often applied by a gravure roll coating method or the like.
  • it can be coated with a roll coater while heating.
  • it is preferable to coat the adhesive of the present invention in a state heated to about room temperature to about 120 ° C. so that the viscosity of the adhesive of the present invention is about 500 to 2500 mPa ⁇ s.
  • the adhesive of the present invention can be used as a water vapor barrier adhesive for various applications that require gas barrier properties, particularly water vapor barrier properties, for polymers, paper, metals, and the like.
  • the adhesive of the present invention can be used as an adhesive for film lamination. Since the laminated film is excellent in gas barrier property, particularly water vapor barrier property, it can be used as a gas barrier property, particularly water vapor barrier laminated film.
  • the film for lamination used in the present invention is not particularly limited, and a thermoplastic resin film can be appropriately selected according to a desired application.
  • a thermoplastic resin film can be appropriately selected according to a desired application.
  • PET film polystyrene film, polyamide film, polyacrylonitrile film
  • polyethylene film LLDPE: low density polyethylene film
  • HDPE high density polyethylene film
  • polypropylene film CPP: unstretched polypropylene film
  • OPP examples thereof include polyolefin films such as biaxially stretched polypropylene film), polyvinyl alcohol films, and ethylene-vinyl alcohol copolymer films. These may be subjected to stretching treatment.
  • the stretching treatment method it is common to perform simultaneous biaxial stretching or sequential biaxial stretching after the resin is melt-extruded by extrusion film forming method or the like to form a sheet. Further, in the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then perform lateral stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.
  • the adhesive of the present invention can be preferably used as an adhesive for a laminated film formed by bonding a plurality of the same or different resin films.
  • the resin film may be appropriately selected depending on the purpose.
  • the outermost layer is a thermoplastic resin film selected from PET, OPP, and polyamide, and the innermost layer is unstretched polypropylene.
  • CPP a composite film consisting of two layers using a thermoplastic resin film selected from a low density polyethylene film (hereinafter abbreviated as LLDPE), or an outermost layer selected from, for example, PET, polyamide and OPP
  • LLDPE low density polyethylene film
  • a three-layer composite using a thermoplastic resin film, a thermoplastic resin film that forms an intermediate layer selected from OPP, PET, and polyamide, and a thermoplastic resin film that forms an innermost layer selected from CPP and LLDPE Heat to form an outermost layer selected from a film, for example, OPP, PET, polyamide Selected from a plastic film, a thermoplastic film forming a first intermediate layer selected from PET and nylon, and a thermoplastic film forming a second intermediate layer selected from PET and polyamide, LLDPE, and CPP
  • a four-layer composite film using a thermoplastic resin film that forms the innermost layer can be preferably used as a food packaging material as a gas barrier property, particularly as a water vapor barrier film.
  • the surface of the film may be subjected to various surface treatments such as flame treatment and corona discharge treatment as necessary so that an adhesive layer free from defects such as film breakage and repellency is formed.
  • the water vapor barrier laminate film of the present invention is obtained by applying the adhesive of the present invention to one of the thermoplastic resin films and then laminating the other thermoplastic resin film and laminating them by lamination.
  • lamination method known lamination such as dry lamination, non-solvent lamination, extrusion lamination, etc. can be used.
  • the adhesive of the present invention is applied to one of the base films by a gravure roll method, and the other base film is stacked and bonded by dry lamination (dry lamination method).
  • the temperature of the laminate roll is preferably about room temperature to 60 ° C.
  • non-solvent lamination is applied to the surface immediately after applying the adhesive of the present invention, which has been heated to room temperature to about 120 ° C., with a roll such as a roll coater heated to room temperature to about 120 ° C.
  • a laminate film can be obtained by laminating various film materials.
  • the laminating pressure is preferably about 10 to 300 kg / cm 2 .
  • the organic solvent solution of the adhesive of the present invention is applied to the base film as an adhesion aid (anchor coating agent) by a roll such as a gravure roll, and the solvent is dried and cured at room temperature to 140 ° C.
  • a laminate film can be obtained by laminating the polymer material melted by the extruder.
  • the polymer material to be melted is preferably a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin.
  • the water vapor barrier laminate film of the present invention is preferably subjected to aging after production. If polyisocyanate is used as a curing agent, the aging condition is from room temperature to 80 ° C. for 12 to 240 hours, during which adhesive strength is generated.
  • a laminate film formed from the adhesive may be a PVDC coat layer, a polyvinyl alcohol (PVA) coat layer, or ethylene-vinyl alcohol.
  • PVDC coat layer a polyvinyl alcohol (PVA) coat layer
  • ethylene-vinyl alcohol a laminate film formed from the adhesive
  • Very high level barrier without using commonly used barrier materials such as copolymer (EVOH) film layer, metaxylylene adipamide film layer, inorganic vapor deposited film layer deposited with alumina, silica, etc. Sex is expressed.
  • a barrier film containing a gas barrier layer such as a polymer or vinylidene chloride may be used in combination.
  • polyester polyol having a number average molecular weight of 640, an acid value of 0.2 mgKOH / g, and a hydroxyl value of 184.4 mgKOH / g.
  • polyester polyol having a number average molecular weight of 720, an acid value of 1.09 mgKOH / g, and a hydroxyl value of 160.5 mgKOH / g.
  • NDoPA polyester polyol
  • the esterification reaction was terminated to obtain a polyester polyol (CHDMODA) having a number average molecular weight of 2000, an acid value of 0.91 mgKOH / g, and a hydroxyl value of 54.5 mgKOH / g.
  • CHDMODA polyester polyol
  • the esterification reaction was terminated to obtain a polyester polyol (EGOSA) having a number average molecular weight of 600, an acid value of 0.55 mgKOH / g, and a hydroxyl value of 190.8 mgKOH / g.
  • EGOSA polyester polyol
  • the internal temperature was stored at 220 ° C.
  • the esterification reaction was terminated to obtain a polyester polyol (PDTMAOcOH) having a number average molecular weight of 600, an acid value of 0.43 mgKOH / g, and a hydroxyl value of 187.4 mgKOH / g.
  • PDTMAOcOH polyester polyol
  • the solvent-type adhesive is subjected to corona treatment of a PET film (“E-5102” manufactured by Toyobo Co., Ltd.) having a thickness of 12 ⁇ m so that the coating amount is about 5 g / m 2 (solid content). It is applied to the surface, the solvent is evaporated and dried with a dryer set at a temperature of 70 ° C., and the adhesive surface of the PET film to which the adhesive is applied, and a nylon film with a thickness of 15 ⁇ m (“Emblem ON” manufactured by Unitika Ltd.) -BC ”) was laminated with a corona-treated surface to prepare a composite film having a layer structure of PET film / adhesive layer / nylon film. Next, this composite film was aged at 40 ° C. for 5 days to cure the adhesive, and the laminated film of the present invention was obtained.
  • a PET film (“E-5102” manufactured by Toyobo Co., Ltd.) having a thickness of 12 ⁇ m so that the coating amount is about 5 g
  • the water vapor barrier property of the adhesive cured coating film alone was calculated using the formula (a) from the measurement results of the water vapor barrier laminated film, PET film and nylon film.
  • P Water vapor transmission rate of water vapor barrier laminate film
  • P1 Water vapor transmission rate of coating film alone
  • P2 Water vapor transmission rate of 12 ⁇ m PET film (calculated as 49 g / m 2 ⁇ 24 hours)
  • P3 Water vapor permeability of 15 ⁇ m nylon film (calculated as 300 g / m 2 ⁇ 24 hours)
  • Table 2 shows the results using the resin compositions obtained in Comparative Examples 1 to 5.
  • the adhesive of the present invention has good adhesive strength and water vapor barrier properties, in addition to the adhesive for film laminate for the packaging material, for example, an adhesive for a protective film for solar cells and a barrier substrate for display elements. It can be suitably used in applications where water vapor barrier properties are desired, such as adhesives for electronic materials such as adhesives, adhesives for building materials, and adhesives for industrial materials.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une composition de résine destinée à être utilisée comme adhésif formant une barrière contre la vapeur. Ladite composition de résine est obtenue en faisant réagir un polyol avec un durcisseur et soit le polyol, soit le durcisseur présente des structures de type tricycloalcane qui représentent 10-50 % de la masse de la composition de résine. Ladite composition de résine permet d'obtenir un film qui présente une excellente adhésivité et d'excellentes performances de barrière contre la vapeur. La présente invention concerne également un stratifié de film formant une barrière contre la vapeur, obtenu par durcissement de la composition de résine susmentionnée sur le dessus d'un film.
PCT/JP2013/083727 2012-12-20 2013-12-17 Composition de résine destinée à être utilisée comme adhésif formant une barrière contre la vapeur et stratifié Ceased WO2014098069A1 (fr)

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JP2016047870A (ja) * 2014-08-27 2016-04-07 Dic株式会社 蒸着面保護用コーティング材、及びガスバリア性フィルム
JP2018522711A (ja) * 2015-05-15 2018-08-16 ダウ グローバル テクノロジーズ エルエルシー ラミネータへの材料送達システム
EP4172227A1 (fr) * 2020-06-25 2023-05-03 Dow Global Technologies LLC Polyol et mousse fabriquée à partir de celui-ci

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JP2016047870A (ja) * 2014-08-27 2016-04-07 Dic株式会社 蒸着面保護用コーティング材、及びガスバリア性フィルム
JP2018522711A (ja) * 2015-05-15 2018-08-16 ダウ グローバル テクノロジーズ エルエルシー ラミネータへの材料送達システム
EP4172227A1 (fr) * 2020-06-25 2023-05-03 Dow Global Technologies LLC Polyol et mousse fabriquée à partir de celui-ci
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TW201432006A (zh) 2014-08-16

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