WO2020071134A1 - Adhésif, stratifié et procédé de production d'un stratifié - Google Patents

Adhésif, stratifié et procédé de production d'un stratifié

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Publication number
WO2020071134A1
WO2020071134A1 PCT/JP2019/036705 JP2019036705W WO2020071134A1 WO 2020071134 A1 WO2020071134 A1 WO 2020071134A1 JP 2019036705 W JP2019036705 W JP 2019036705W WO 2020071134 A1 WO2020071134 A1 WO 2020071134A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive
compound
laminate
acid
mass
Prior art date
Application number
PCT/JP2019/036705
Other languages
English (en)
Japanese (ja)
Inventor
茜 笹本
常行 手島
竜二 木村
浩平 中根
Original Assignee
Dic株式会社
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株式会社 filed Critical Dic株式会社
Publication of WO2020071134A1 publication Critical patent/WO2020071134A1/fr

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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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • C09J175/08—Polyurethanes from polyethers

Definitions

  • the present invention relates to an adhesive having excellent adhesiveness, a laminate using the adhesive, and a method for producing the laminate.
  • the mainstream packaging material for retort pouches is obtained by laminating a plurality of films, and various plastic films, metal films, metal-deposited films and the like are used as the films.
  • An adhesive is used when bonding films of different materials.
  • the adhesive often contains a solvent, and there has been a problem that VOCs are generated and the solvent is eluted into the contents during the retort sterilization treatment.
  • An object of the present invention is to provide an adhesive having excellent adhesiveness, particularly an adhesive having excellent adhesiveness and wet heat resistance even without solvent, and a laminate using the adhesive.
  • the polyol compound is a polyester polyol or a polyether polyol, the weight-average molecular weight of the monol compound is 300 to 1800, and the ratio of the monol compound to the total amount of the hydroxyl group-containing compound is 30 to 50 wt%.
  • An adhesive is provided.
  • a laminate comprising the first base material, the adhesive layer of the present invention, and the second base material in this order.
  • one of the first substrate and the second substrate is a metal or a metal oxide, and the other substrate is a plastic.
  • a method for producing a laminate comprising: applying the adhesive of the present invention to a first base material to form an adhesive layer; and laminating a second base material to the adhesive layer.
  • a method for producing a laminate comprising: applying the adhesive of the present invention to a first base material to form an adhesive layer; and laminating a second base material to the adhesive layer.
  • the composition of the present invention it is possible to provide an adhesive excellent in adhesiveness, particularly an adhesive excellent in both adhesiveness and wet heat resistance, and a laminate having the adhesive layer. .
  • the adhesive of the present invention is excellent in initial adhesiveness, and thus can be favorably used as an adhesive for lamination.
  • the present invention can provide an adhesive which is excellent in wet heat resistance and which is excellent even when a different material such as metal and plastic is used as a base material, the present invention is suitably used particularly as an adhesive for producing a retort packaging sheet. It is possible.
  • the present invention is an adhesive containing a hydroxyl group-containing compound and a polyurethane polyisocyanate, wherein the hydroxyl group-containing compound contains a polyol compound and a monol compound,
  • the polyol compound is a polyester polyol or a polyether polyol,
  • the adhesive is characterized in that the monol compound has a weight average molecular weight of 300 to 1800, and the ratio of the monol compound to the total amount of the hydroxyl group-containing compound is 30 to 50 wt%.
  • the hydroxyl group-containing compound in the present invention is a general term for compounds having one or more hydroxyl groups in a molecule.
  • the hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group, but is preferably an alcoholic hydroxyl group from the viewpoint of reactivity.
  • the present invention is characterized by containing a polyol compound and a monol compound.
  • the polyol compound is a compound having two or more alcoholic hydroxyl groups.
  • the polyol compound of the present invention is particularly characterized in that it is a polyester polyol and / or a polyether polyol. One of these polyols may be used alone, or two or more may be used in combination.
  • polyester polyol examples include a reaction product of a dicarboxylic acid or a polycarboxylic acid (or a salt thereof, or an acid anhydride) and a polyhydric alcohol, or a ring-opening polymer of caprolactone.
  • the dicarboxylic acids include aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, succinic acid, and glutaric acid, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, and isophthalic acid.
  • Aromatic dicarboxylic acids such as dicarboxylic acids, and anhydrides of these dicarboxylic acids, and as polyvalent carboxylic acids, aromatic polycarboxylic acids such as pyromellitic acid and trimellitic acid, and anhydrides of these polycarboxylic acids are applied. And they can be used alone or in a mixture of two or more.
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, and tetraethylene.
  • alkylene diols having 1 to 12 carbon atoms such as glycol and dipropylene glycol
  • diols having a carboxylic acid such as 2,2-bis (hydroxymethyl) propionic acid.
  • examples of the latter include ring-opening polymers such as ⁇ -caprolactam, ⁇ -valerolactam, and ⁇ -propyrolactam.
  • polyether polyols examples include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, polyethylene glycol / polypropylene glycol block copolymer, propylene glycol propylene oxide adduct, bisphenol A propylene oxide adduct, glycerin propylene oxide adduct, ethylene diamine
  • propylene oxide adducts examples include propylene oxide adducts, ethylenediamine propylene oxide adducts, sorbitol-based propylene oxide adducts, sucrose-based propylene oxide adducts, and propylene oxide / ethylene oxide random polyether.
  • the polyester polyol or the polyether polyol may have a urethane extension as required.
  • the polyisocyanate used for urethane elongation is not particularly limited, and known and commonly used ones can be used.
  • an aromatic polyisocyanate, an aliphatic or alicyclic polyisocyanate, a blocked isocyanate, or a modified product thereof can be used.
  • One of these polyisocyanates may be used alone, or two or more may be used in combination.
  • the monol compound is a compound having one alcoholic hydroxyl group.
  • the monol compound of the present invention is characterized by having a weight average molecular weight of 300 to 1800.
  • the main chain of the monol compound is not particularly limited, and may be a vinyl resin, an acrylic resin, an ester resin, an epoxy resin, a urethane resin, or the like. Further, aliphatic alcohols, alkylene glycols and the like may be used. Preferred are a hydroxyl group-containing acrylic resin, an aliphatic alcohol, and an alkylene glycol.
  • the structure of the monol compound of the present invention may be linear or branched.
  • the bonding position of the hydroxyl group is not particularly limited, but is preferably present at the terminal of the molecular chain.
  • the monol compound of the present invention includes, for example, hydroxyl group-containing polymethyl acrylate, hydroxyl group-containing polybutyl acrylate, octanol, dodecanol, etc., and is preferably polypropylene glycol monomethyl ether or polypropylene monobutyl ether.
  • the monol compound of the present invention is characterized in that it is 30 to 50% by weight based on the total amount of the hydroxyl group-containing compound of the present invention. If the amount is less than 30 wt%, the adhesive becomes rigid and cannot follow the temperature change. On the other hand, if it is more than 50 wt%, the crosslinking is insufficient and the adhesiveness is poor. Preferably it is 35 wt% or more and 45 wt% or less.
  • the adhesive of the present invention contains a polyurethane polyisocyanate.
  • the polyurethane polyisocyanate is a compound having a urethane bond and two or more isocyanate groups in a molecule. By containing a polyurethane polyisocyanate, it reacts with a hydroxyl group-containing compound such as a polyol or a monool to form a urethane bond, thereby exhibiting high adhesiveness.
  • Polyurethane polyisocyanate is obtained by reacting a polyisocyanate compound with a hydroxyl group of a polyol.
  • polystyrene resin examples include a polyester polyol and a polyether polyol.
  • One of these polyols may be used alone, or two or more may be used in combination.
  • polyester polyol examples include a reaction product of a dicarboxylic acid or a polycarboxylic acid (or a salt thereof, or an acid anhydride) and a polyhydric alcohol, or a ring-opening polymer of caprolactone.
  • the dicarboxylic acids include aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, succinic acid, and glutaric acid, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, and isophthalic acid.
  • Aromatic dicarboxylic acids such as dicarboxylic acids, and anhydrides of these dicarboxylic acids, as polycarboxylic acids, aromatic polycarboxylic acids such as pyromellitic acid and trimellitic acid, and anhydrides of these polycarboxylic acids are used. And they can be used alone or in a mixture of two or more.
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, and tetraethylene.
  • alkylene diols having 1 to 12 carbon atoms such as glycol and dipropylene glycol
  • diols having a carboxylic acid such as 2,2-bis (hydroxymethyl) propionic acid.
  • examples of the latter include ring-opening polymers such as ⁇ -caprolactam, ⁇ -valerolactam, and ⁇ -propyrolactam.
  • polyether polyols examples include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, polyethylene glycol / polypropylene glycol block copolymer, propylene glycol propylene oxide adduct, bisphenol A propylene oxide adduct, glycerin propylene oxide adduct, ethylene diamine
  • propylene oxide adducts examples include propylene oxide adducts, ethylenediamine propylene oxide adducts, sorbitol-based propylene oxide adducts, sucrose-based propylene oxide adducts, and propylene oxide / ethylene oxide random polyether.
  • the polyisocyanate compound used for the polyurethane polyisocyanate is not particularly limited, and examples thereof include an aromatic structure in the molecular structure of tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate and the like.
  • diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, and 4,4'-methylenebis (cyclohexyl isocyanate) are exemplified.
  • Polyisocyanates having an alicyclic structure or an aromatic structure in their molecular structure are preferred from the viewpoint that an adhesive having excellent lamination strength and curability can be obtained.
  • the linear aliphatic polyisocyanate and the allophanate compound, the isocyanurate of these polyisocyanates, and the allophanate derivative derived from these polyisocyanates can also impart flexibility to the laminate and increase retort resistance. preferable.
  • the reaction ratio of the polyisocyanate compound and the polyol component is such that the equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group to the hydroxyl group in the polyol component is in the range of 1.5 to 5.0. It is preferable from the viewpoint that the viscosity of the adhesive is in an appropriate range and the coatability is good.
  • the adhesive of the present invention may contain other polyisocyanates in addition to the polyurethane polyisocyanate.
  • Other polyisocyanates are not particularly limited, and known and commonly used ones can be used. Any other polyisocyanate may be a compound having two or more isocyanate groups. Examples of the polyisocyanate include an aromatic polyisocyanate, an aliphatic or alicyclic polyisocyanate, a blocked isocyanate, and a modified product thereof.
  • One of these polyisocyanates may be used alone, or two or more may be used in combination.
  • the other polyisocyanate is preferably 40% by weight or less based on the total amount of the polyisocyanate in the adhesive in order to obtain a sufficient pot life when mixed with the polyol.
  • the adhesive of the present invention adheres by reacting the contained hydroxyl group-containing compound with polyisocyanate.
  • the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the hydroxyl group-containing compound is preferably 0.5 to 10, more preferably 1.5 to 5.0. . If the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the hydroxyl group-containing compound is within the above range, the adhesiveness and the moist heat resistance will be better.
  • the adhesive of the present invention can be used without using a solvent, but may contain a solvent according to the intended use.
  • the solvent include organic solvents, for example, methyl ethyl ketone, acetone, ethyl acetate, butyl acetate, toluene, dimethylformamide, acetonitrile, methyl isobutyl ketone, methanol, ethanol, propanol, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, Propylene glycol monomethyl ether acetate and the like.
  • the type and amount of the solvent may be appropriately selected depending on the intended use.
  • the adhesive of the present invention may use a pigment, if necessary.
  • the pigment that can be used in this case is not particularly limited.
  • examples of the pigment include organic pigments and inorganic pigments such as pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearlescent pigments, and further, plastic pigments.
  • specific examples of these colorants include various pigments.
  • organic pigments include various insoluble azo pigments such as benzidine yellow, Hansa yellow, and Lake 4R; and solubility of lake C, carmine 6B, Bordeaux 10 and the like.
  • Azo pigments various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various chlorinated dyeing lakes such as rhodamine lake and methyl violet lake; various mordant dye pigments such as quinoline lake and fast sky blue; anthraquinone Vat dyes such as thioindigo pigments and perinone pigments; various quinacridone pigments such as synchasia red B; various oxazine pigments such as oxazine violet; various condensed azos such as chromophtal Pigment; aniline black, etc. And the like.
  • the inorganic pigments include various chromates such as graphite, zinc chromate, and molybdate orange; various ferrocyan compounds such as navy blue; titanium oxide, zinc white, mapico yellow, iron oxide, red iron oxide, and chrome oxide.
  • Various metal oxides such as green and zirconium oxide; various sulfides or selenides such as cadmium yellow, cadmium red and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types of calcium silicate and ultramarine blue
  • Various carbonates such as calcium carbonate and magnesium carbonate; Various phosphates such as cobalt violet and manganese purple;
  • Various metal powders such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder Pigments; flake pigments of these metals, mica flake pigments; mica flakes coated with metal oxide Click pigments, micaceous iron oxide pigments such as metallic pigment and pearl pigment; graphite, carbon black and
  • the extender pigment for example, precipitated barium sulfate, powder, precipitated calcium carbonate, calcium bicarbonate, dolomite, alumina white, silica, hydrated fine powdered silica (white carbon), ultrafine powdered anhydrous silica (Aerosil), silica sand (silica) Sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess and the like.
  • plastic pigment examples include “Grandol PP-1000” and “PP-2000S” manufactured by DIC Corporation.
  • inorganic oxides such as titanium oxide and zinc white as a white pigment, and carbon black as a black pigment are more preferable because of excellent durability, weather resistance and design.
  • the mass ratio of the pigment used in the present invention is 1 to 400 parts by mass, preferably 10 to 300 parts by mass, based on 100 parts by mass of the total of the hydroxyl group-containing compound and the polyurethane polyisocyanate. It is more preferable because it is excellent.
  • the adhesive of the present invention can also use an adhesion promoter.
  • the adhesion promoter include a silane coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, and an epoxy resin.
  • silane coupling agent examples include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, and N- ⁇ (aminoethyl) - ⁇ Aminosilanes such as -aminopropyltrimethyldimethoxysilane and N-phenyl- ⁇ -aminopropyltrimethoxysilane; ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -gly Epoxy silanes such as sildoxypropyltriethoxysilane; vinylsilanes such as vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇
  • titanate-based coupling agents include, for example, tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium and the like can be mentioned.
  • examples of the aluminum-based coupling agent include acetoalkoxyaluminum diisopropylate and the like.
  • Epoxy resins include generally commercially available epbis type, novolak type, ⁇ -methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, Various epoxy resins such as polycarboxylic acid ester type, aminoglycidyl type, resorcinol type and the like can be mentioned.
  • the adhesive of the present invention may contain various additives as long as the effects of the present invention are not impaired.
  • the additive include a leveling agent; inorganic fine particles such as colloidal silica and alumina sol; organic fine particles of polymethyl methacrylate; an antifoaming agent; a sagging inhibitor; a wetting and dispersing agent; Deactivator; Peroxide decomposer; Flame retardant; Reinforcing agent; Plasticizer; Lubricant; Rust inhibitor; Fluorescent brightener; Inorganic heat ray absorber; Flame retardant; Examples thereof include an aromatic vinyl / maleic anhydride copolymer.
  • These pigments, adhesion promoters and additives can be mixed with either one of the hydroxyl group-containing compound and the polyurethane polyisocyanate, or can be used by mixing at the time of coating.
  • the laminate of the embodiment is a laminate having a three-layer structure or more including a first base material, the adhesive layer, and a second base material.
  • the materials of the first base material and the second base material are not particularly limited, and may be appropriately selected depending on the use. Examples thereof include wood, metal, metal oxide, plastic, paper, silicon, and modified silicon. It may be a substrate obtained by joining materials.
  • the shape of the substrate is not particularly limited, and may be an arbitrary shape according to the purpose, such as a flat plate, a sheet, or a surface having a curvature on the entire surface or a part thereof. There is no limitation on the hardness, thickness, etc. of the substrate.
  • Each substrate may be a resin alone or may contain other compounds. As the other compound, the same compound as the above-mentioned compound for the adhesive may be used.
  • the surface of each substrate may be printed. The printing surface may be on the adhesive layer side or may be formed on the outside.
  • the plastic substrate is not particularly limited as long as it is made of plastic.
  • PET polyethylene terephthalate
  • nylon film polyethylene terephthalate
  • OPP biaxially oriented polypropylene
  • CPP unoriented polypropylene
  • LLDPE linear Low-density polyethylene
  • metal and metal oxide substrates examples include aluminum, chromium, zinc, gold, silver, platinum, nickel, SiO2, TiO2, ZrO2, and the like.
  • the metal and metal oxide substrates may be formed by vapor deposition.
  • the first base material and the second base material may be the same or different materials. Since the adhesive of the present invention is excellent in adhesiveness, it can be satisfactorily adhered to different materials. For example, a good laminate can be obtained even with a combination of plastic and metal.
  • the layer configuration of the laminate is not particularly limited, but the adhesive of the present invention can be suitably used for a laminate having a metal or metal oxide layer since it can be suitably bonded to metal and metal oxide.
  • a laminate used as a retort packaging sheet is preferably a laminate having a metal or metal oxide layer, the adhesive layer of the present invention, and a plastic layer.
  • the first base material is a metal or metal oxide layer such as an aluminum foil or an aluminum vapor-deposited film
  • the second base material has a layer structure formed of a plastic layer such as nylon, polyethylene terephthalate, or CPP. Laminates are preferred.
  • a sealant film can be prepared by having a sealant layer in the layer configuration.
  • a sealant film having a layer structure of a plastic layer, a first adhesive layer, a metal or metal oxide layer, a second adhesive layer, and a sealant layer is given as an example.
  • the laminate may have a layer configuration of four or more layers.
  • the adhesive layer of the present invention may be one layer or two or more layers.
  • a layer configuration of five or more layers of a first base material-a first adhesive layer-a second base material-a second adhesive layer-a third base material is preferable.
  • the combination of the first substrate / second substrate / third substrate may be PET / aluminum / LLDPE, nylon / aluminum / LLDPE, PET / aluminum / CPP.
  • the adhesive of the present invention may be the first adhesive layer or the second adhesive layer, and both may contain the adhesive of the present invention. Further, a laminate having a layer configuration of six or more layers may of course be used.
  • the laminate of the present invention has a step of applying the adhesive of the present invention on a first substrate, and a step of subsequently laminating a second substrate.
  • a spray method a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, a doctor blade method, a curtain coating method, a slit coating method, a screen printing method, An ink jet method and the like can be mentioned.
  • the adhesive of the present invention has very high adhesive strength, it can be suitably used for lamination.
  • the laminating method include a method in which the present adhesive is applied to a first base material by a roll coating method, and then the second base material is bonded without going through a drying step.
  • the coating weight is preferably in the range of 0.5 to 10.0 g / m 2 , more preferably 1.5 to 4.0 g / m 2 . When the content is 1.5 g / m 2 or more, the adhesiveness is good, and when the content is 4.0 g / m 2 or less, the winding property after lamination is good. I have.
  • the laminated laminate of the present invention is subjected to aging after production.
  • the aging conditions are preferably a temperature of 15 to 60 ° C. and a time of 6 to 168 hours, during which the adhesive strength is generated.
  • the adhesive of the present invention exhibits high adhesiveness and wet heat resistance, it can be suitably used as an adhesive for lamination, and the obtained laminate can be particularly suitably used as a sheet for retort packaging.
  • the number average molecular weight was measured using a gel permeation chromatograph (GPC) under the following conditions.
  • HA-220B Dick Dry HA-220B (manufactured by DIC Graphics Co., Ltd.)
  • HA-500B Dick Dry HA-500B (manufactured by DIC Graphics Co., Ltd.)
  • HA-400B Dick Dry HA-400B (manufactured by DIC Graphics Co., Ltd.)
  • HA-700B Dick Dry HA-700B (manufactured by DIC Graphics Co., Ltd.)
  • UMM-1001 Actflow UMM-1001 (weight average molecular weight 1000, Soken Chemical Co., Ltd.)
  • UMM-1001-2 Actflow UMM-1001-2 (weight average molecular weight 2000, Soken Chemical Co., Ltd.)
  • MP-40 Smack MP-40 (weight average molecular weight 400, Kao Corporation)
  • MP-70 Smack MP-70 (weight average molecular weight 700, Kao Corporation)
  • EHDG (weight average molecular weight 220, 2-ethylhexyl diglycol, Nippon Emulsifier Co., Ltd.) Lauryl alcohol: Calcol 2098 (weight average molecular weight 190, Kao Corporation)
  • 2K-SF-220A Dick Dry 2K-SF-220A (manufactured by DIC Graphics Co., Ltd.)
  • 2K-SF-400A Dick Dry 2K-SF-400A (manufactured by DIC Graphics Co., Ltd.)
  • 2K-SF-700A Dick Dry 2K-SF-700A (manufactured by DIC Graphics Co., Ltd.)
  • Synthesis Example 1 [Synthesis of polyester polyol resin (A1)] 154 parts by mass of ethylene glycol, 99 parts by mass of neopentyl glycol, and 134 parts by mass of 1,6-hexanediol were charged into a reaction vessel, and heated to 80 ° C. while stirring under a stream of nitrogen gas. While stirring, 537 parts by mass of isophthalic acid and 70 parts by mass of sebacic acid were charged into a reaction vessel and heated to 150 ° C. to 240 ° C. to carry out an esterification reaction. When the acid value became 5 mgKOH / g or less, the pressure in the reaction vessel was gradually reduced, and the reaction was carried out at 200 to 240 ° C.
  • polyester polyol resin (A1)) was obtained.
  • Synthesis Example 2 [Synthesis of polyester polyol resin (A2)] A reaction vessel was charged with 304 parts by mass of 2-methyl-propanediol, 190 parts by mass of ethylene glycol, and 52 parts by mass of trimethylolpropane, and dissolved by heating to 80 ° C. while stirring under a stream of nitrogen gas. While stirring, 81 parts by mass of isophthalic acid and 640 parts by mass of adipic acid were charged into a reaction vessel and heated to 150 ° C. to 240 ° C. to carry out an esterification reaction.
  • polyester polyol resin (A2) A polyester polyol resin (hereinafter, abbreviated as “polyester polyol resin (A2)”) was obtained.
  • Synthesis Example 3 [Synthesis of polyurethane polyisocyanate (B1)] 121 parts by mass of ethylene glycol, 107 parts by mass of neopentyl glycol, 132 parts by mass of 1,6-hexanediol, and 92 parts by mass of 3-methyl-1,5-pentanediol are charged into a reaction vessel, and stirred under a nitrogen gas stream. Heated to 80 ° C. With further stirring, 270 parts by mass of isophthalic acid and 278 parts by mass of sebacic acid were charged into a reaction vessel and heated to 150 ° C. to 240 ° C. to carry out an esterification reaction.
  • intermediate B1 ′ A polyester polyol resin (hereinafter, abbreviated as “intermediate B1 ′”) was obtained.
  • 160 parts by mass of xylylene diisocyanate, 369 parts by mass of hexamethylene diisocyanate allophanate and 97 parts by mass of hexamethylene diisocyanurate are charged to the reaction vessel with respect to 374 parts by mass of the intermediate B1 ', and the mixture is stirred under a nitrogen gas stream. The mixture was heated to 85 ° C.
  • polyurethane polyisocyanate (B1)”) Abbreviated
  • Synthesis Example 4 [Synthesis of polyurethane polyisocyanate (B2)] 159 parts by mass of ethylene glycol and 250 parts by mass of 2-methyl-propanediol were charged into a reaction vessel and dissolved by heating to 80 ° C. while stirring under a stream of nitrogen gas. Further, 591 parts by mass of adipic acid was charged into a reaction vessel while stirring, and heated to 150 ° C. to 240 ° C. to perform an esterification reaction. When the acid value becomes 5 mgKOH / g or less, the pressure in the reaction vessel is gradually reduced, and the reaction is carried out at 200 to 220 ° C. for 1 hour at 1 mmHg or less.
  • the acid value is 0.8 mgKOH / g and the molecular weight is about 620.
  • a polyester polyol resin (hereinafter, abbreviated as “intermediate B2 ′”) was obtained.
  • intermediate B2 ′ A polyester polyol resin
  • 4'-diphenylmethane diisocyanate was added to '402 parts by mass of the intermediate B2, and an MDI mixture ["Lupranate MI” manufactured by BASF, 4,4'-diphenylmethane diisocyanate / 2,4'-diphenylmethane]
  • a mixture of diisocyanate (mass ratio) 1/1, NCO group content of 33.3 g / 100 g or more] 493 parts by mass is charged into a reaction vessel, and heated to 85 ° C.
  • polyurethane isocyanate (B2) A bifunctional polyisocyanate having an isocyanate% by titration (using di-n-butylamine) of 14.5% by mass (hereinafter abbreviated as "polyurethane isocyanate (B2)") was obtained.
  • Synthesis Example 5 [Synthesis of polyurethane polyisocyanate (B3)] 448 parts by mass of diethylene glycol and 15 parts by mass of trimethylolpropane were charged in a reaction vessel, and dissolved by heating to 80 ° C. while stirring under a nitrogen gas stream. While stirring, 537 parts by mass of adipic acid was charged into a reaction vessel and heated to 150 ° C. to 240 ° C. to carry out an esterification reaction. When the acid value becomes 5 mgKOH / g or less, the pressure in the reaction vessel is gradually reduced, and the reaction is carried out at 200 to 220 ° C. for 1 hour at 1 mmHg or less.
  • the acid value is 0.8 mgKOH / g and the molecular weight is about 1270.
  • a polyester polyol resin (hereinafter, abbreviated as “intermediate B3 ′”) was obtained. Then, based on 496 parts by mass of the intermediate B3 ', 116 parts by mass of 4,4'-diphenylmethane diisocyanate, an MDI mixture ["Lupranate MI" manufactured by BASF, 4,4'-diphenylmethane diisocyanate / 2,4'-diphenylmethane] A mixture having a diisocyanate (mass ratio) of 1/1, an NCO group content of at least g / 100 g], 368 parts by mass, and a styrene / maleic anhydride copolymer (SMA2000, Clay Valley Co., Ltd.) of 19 parts by mass were charged into a reaction vessel.
  • SMA2000 styrene / maleic anhydride copolymer
  • Synthesis Example 6 [Synthesis of polyurethane polyisocyanate (B4)] 480 parts by mass of diethylene glycol was charged into a reaction vessel and heated to 80 ° C. while stirring under a nitrogen gas stream. Further, with stirring, 520 parts by mass of adipic acid was charged into a reaction vessel and heated to 150 ° C. to 240 ° C. to perform an esterification reaction. When the acid value becomes 5 mgKOH / g or less, the pressure in the reaction vessel is gradually reduced, and the reaction is carried out at 1 mmHg or less at 200 to 240 ° C. for 1 hour. The acid value is 0.8 mgKOH / g and the molecular weight is about 840.
  • a polyester polyol resin (hereinafter, abbreviated as “intermediate B4 ′”) was obtained.
  • intermediate B4 ′ A polyester polyol resin
  • 417 parts by mass of m-xylene diisocyanate and 20 parts by mass of a styrene / maleic anhydride copolymer (“SMA2000”, Clay Valley Co.) were charged into a reaction vessel.
  • SMA2000 styrene / maleic anhydride copolymer
  • the mixture was heated to 85 ° C. with stirring under a stream of nitrogen gas and reacted for about 10 hours to obtain a bifunctional polyisocyanate having an isocyanate% of 13.5% by mass (hereinafter, abbreviated as “polyurethane isocyanate (B4)”).
  • SMA2000 styrene / maleic anhydride copolymer
  • a polyethylene terephthalate (PET) film (“Ester Film E5102”, 12 ⁇ m, manufactured by Toyobo Co., Ltd.) was gravure printed with a printing ink (“Univia NT”, manufactured by DIC Corporation)
  • An adhesive was applied so that the applied amount was about 2.0 g / m 2 of solid content, and the coated surface of this film was bonded to a nylon film (“Emblem ONBC” manufactured by Unitika Ltd., 15 ⁇ m) with a laminator.
  • an adhesive is applied to the nylon surface of the laminated film so that the applied amount becomes about 2.0 g / m 2 of solid content, and the coated surface of this film and an aluminum foil (“Aluminum foil—Toyo Aluminum Co., Ltd. O material “9 ⁇ m) and stored in a thermostat at 40 ° C. for 3 days. Then, it was bonded to the aluminum foil surface with a non-axially stretched polypropylene (CPP) film (“Torayfan ZK93KM” 70 ⁇ m, manufactured by Toray Film Processing Co., Ltd.). This composite film was stored in a thermostat at 40 ° C. for 3 days to complete the laminate of the present invention.
  • CPP non-axially stretched polypropylene
  • ⁇ Lamination strength evaluation method> The laminate was cut into 15 mm widths, and the adhesive strength (N / 15 mm) was measured by a T-type peeling method using a Tensilon universal testing machine manufactured by Orientec Co., at an atmosphere temperature of 25 ° C. and a peeling speed of 300 mm / min.
  • the laminating strength is preferably higher than 4 N / 15 mm, more preferably 5 N / 15 mm or more.
  • Evaluation Evaluation of no peeling ⁇ : Evaluation of 1 or less peeled area ⁇ : Evaluation of 5 or less peeled area Evaluation ⁇ : 6 or more peeled area

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un adhésif comprenant des composés hydroxylés et un polyisocyanate de polyuréthane, les composés hydroxylés comprenant un ou plusieurs composés de polyol et un ou plusieurs composés de monool, les composés de polyol comprenant un polyol de polyester et/ou un polyol de polyéther et les composés de monool ayant un poids moléculaire moyen en poids de 300 à 1 800 et représentant de 30 à 50 % en poids de la quantité totale des composés hydroxylés ; et un stratifié qui comprend un premier substrat, une couche de l'adhésif et un second substrat dans cet ordre.
PCT/JP2019/036705 2018-10-01 2019-09-19 Adhésif, stratifié et procédé de production d'un stratifié WO2020071134A1 (fr)

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Publication number Priority date Publication date Assignee Title
JPWO2021256270A1 (fr) * 2020-06-18 2021-12-23
WO2021256254A1 (fr) * 2020-06-17 2021-12-23 東ソー株式会社 Composition de polyisocyanate modifié et composition de revêtement l'utilisant
JPWO2022172840A1 (fr) * 2021-02-15 2022-08-18

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JPH08183943A (ja) * 1994-12-28 1996-07-16 Sakata Corp ドライラミネート用接着剤組成物およびそれを用いたドライラミネート加工方法
JP2004115681A (ja) * 2002-09-27 2004-04-15 Toyo Ink Mfg Co Ltd 無溶剤型接着剤組成物及びその利用
JP2006037038A (ja) * 2004-07-30 2006-02-09 Toyo Ink Mfg Co Ltd 接着剤組成物
JP2016121351A (ja) * 2014-12-24 2016-07-07 東洋インキＳｃホールディングス株式会社 接着剤組成物および積層体

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Publication number Priority date Publication date Assignee Title
JPH08183943A (ja) * 1994-12-28 1996-07-16 Sakata Corp ドライラミネート用接着剤組成物およびそれを用いたドライラミネート加工方法
JP2004115681A (ja) * 2002-09-27 2004-04-15 Toyo Ink Mfg Co Ltd 無溶剤型接着剤組成物及びその利用
JP2006037038A (ja) * 2004-07-30 2006-02-09 Toyo Ink Mfg Co Ltd 接着剤組成物
JP2016121351A (ja) * 2014-12-24 2016-07-07 東洋インキＳｃホールディングス株式会社 接着剤組成物および積層体

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021256254A1 (fr) * 2020-06-17 2021-12-23 東ソー株式会社 Composition de polyisocyanate modifié et composition de revêtement l'utilisant
JPWO2021256270A1 (fr) * 2020-06-18 2021-12-23
WO2021256270A1 (fr) * 2020-06-18 2021-12-23 Dic株式会社 Agent adhésif, stratifié, procédé permettant de fabriquer un stratifié, et matériau d'emballage
CN115461424A (zh) * 2020-06-18 2022-12-09 Dic株式会社 粘接剂、层叠体、层叠体的制造方法、包装材料
JP7207609B2 (ja) 2020-06-18 2023-01-18 Dic株式会社 接着剤、積層体、積層体の製造方法、包装材
JP2023024587A (ja) * 2020-06-18 2023-02-16 Dic株式会社 接着剤、積層体、積層体の製造方法、包装材
JPWO2022172840A1 (fr) * 2021-02-15 2022-08-18
WO2022172840A1 (fr) * 2021-02-15 2022-08-18 Dic株式会社 Dispositif et procédé de production de film stratifié, adhésif de durcissement en deux parties et film stratifié
JP7343063B2 (ja) 2021-02-15 2023-09-12 Dic株式会社 積層フィルム製造装置、積層フィルムの製造方法、二液硬化型接着剤、積層フィルム

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