WO2006109395A1 - Adhesive for laminate - Google Patents

Adhesive for laminate Download PDF

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Publication number
WO2006109395A1
WO2006109395A1 PCT/JP2006/305107 JP2006305107W WO2006109395A1 WO 2006109395 A1 WO2006109395 A1 WO 2006109395A1 JP 2006305107 W JP2006305107 W JP 2006305107W WO 2006109395 A1 WO2006109395 A1 WO 2006109395A1
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WO
WIPO (PCT)
Prior art keywords
acid
polyester polyol
adhesive
molecule
polyurethane resin
Prior art date
Application number
PCT/JP2006/305107
Other languages
French (fr)
Japanese (ja)
Inventor
Yukihiro Morikawa
Tadayuki Kawaguchi
Takanori Kobayashi
Takashi Taguchi
Original Assignee
Nippon Polyurethane Industry 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 Nippon Polyurethane Industry Co., Ltd. filed Critical Nippon Polyurethane Industry Co., Ltd.
Priority to CN2006800093156A priority Critical patent/CN101146883B/en
Publication of WO2006109395A1 publication Critical patent/WO2006109395A1/en

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Classifications

    • 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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • 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
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes

Definitions

  • the present invention relates to an adhesive particularly suitable for dry lamination of a film of metal or the like.
  • an adhesive used for laminating such a film in general, it has excellent adhesion performance, cold resistance, and heat resistance, and has a wide range of application to substrates such as various plastics and metal foils.
  • Two-component polyurethane adhesives consisting of a main agent having an active hydrogen group such as a hydroxyl group and a curing agent having an isocyanate group have become mainstream.
  • the current two-component polyurethane laminate adhesive requires a curing acceleration process called aging because the curing reaction of the adhesive after bonding is very slow. Specifically, it is necessary to cure the adhesive by storing and aging the laminated film in a 35-60 ° C storage room for about 3-5 days. At this time, since the degree of curing of the adhesive varies depending on the aging conditions, it may affect the adhesive strength of the laminating film. If the aging is insufficient, delamination due to poor curing of the adhesive ( May cause delamination. Particularly in the case of an aliphatic polyurethane adhesive, this curing reaction takes a considerably long time. Therefore, such an aging process is an indispensable process in the dry lamination process, and there is an expense such as capital investment for the installation of a greenhouse for aging and utility for the subsequent heat insulation. It was necessary.
  • Patent Document 1 describes (a) diethylene glycol-based polyester polyol polyol and ( There has been proposed an adhesive for dry laminate containing b) a carboxyl group-containing aromatic polyester polyol and (c) a polyisocyanate. This (b) force Since a ruboxyl group-containing aromatic polyester polyol is obtained by reacting a polyester polyol with a water-free aromatic polyvalent carboxylic acid, the molecular end of the polyester polyol is a carboxyl group.
  • the laminated film packaging material manufactured using the dry laminate adhesive disclosed in Patent Document 1 is filled with food or pharmaceuticals as the contents and used for high temperature processing such as boiling and retort.
  • high temperature processing such as boiling and retort.
  • the content performance such as adhesion performance, hot water resistance, and acid resistance could be improved, the appearance (peeling) of finoleum after high temperature treatment was rather deteriorated.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2000-154365
  • An object of the present invention is to provide an adhesive for laminating with excellent productivity and workability with high initial adhesiveness while maintaining excellent content resistance performance.
  • the inventors of the present invention use (A) a rigid polyester polyol containing an aromatic ring in the molecule and (B) another flexible polyester polyol as a raw material for a polyurethane resin that is a main component of the main agent.
  • the present inventors have found that the above problem can be solved by introducing a carboxyl group at a specific site in the resin, and have completed the present invention.
  • the present invention includes the following (1) to (3).
  • a laminating adhesive comprising: a main agent solution containing a silane coupling agent and an organic solvent; and an isocyanate curing agent.
  • Polyesterol having an aromatic ring in the molecule and having substantially a hydroxyl group at the molecular end
  • Laminate films such as plastic films and metal foils produced using the laminating adhesive of the present invention have excellent peel resistance and adhesion such as initial peel adhesive strength and normal peel adhesive strength. The performance is also excellent. In addition, it was confirmed that there was no abnormality such as delamination in the appearance of the laminate film after boiling or retort treatment, and that it maintained practical adhesive strength. As a result, in film production, tunneling can prevent the film from shifting, and the productivity and workability are also improved.
  • the productivity and workability of the laminate film are greatly improved, and the cost can be reduced and the delivery time can be shortened.
  • the laminating adhesive of the present invention comprises at least a main agent solution and an isocyanate curing agent.
  • the main agent solution in the present invention contains a polyurethane resin, a silane coupling agent, and an organic solvent.
  • the polyurethane resin in the main agent solution comprises (A) a polyester polyol having an aromatic ring in the molecule and a molecular end substantially having a hydroxyl group, and (B) a polyester polyol having no aromatic ring in the molecule, polyester polyol ( It is obtained by reacting C) dimethylolalkanoic acid with (D) organic polyisocyanate.
  • (A) Mass ratio of polyester polyol having an aromatic ring in the molecule and a molecular terminal substantially having a hydroxyl group and (B) polyester polyol not having an aromatic ring in the molecule (A) / (B) Is from 95/5 to 75/25.
  • Polyester polyol contains an aromatic ring in the molecule, but the molecular terminal is substantially a hydroxyl group (that is, a carboxyl group does not substantially exist at the molecular terminal, ).
  • the acid value of the polyester polyol is preferably 1 mgK0H / g or less.
  • polyester polyols include terephthalic acid and isophthalanol.
  • a polyester polyol obtained by a dehydration condensation reaction of an aromatic dicarboxylic acid such as an acid, its acid ester, an acid anhydride, and the like with a polyol, or the aromatic dicarboxylic acid, its acid ester, an acid anhydride, etc., and a succinic acid, Polyester obtained by dehydration condensation reaction of non-aromatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, acid esters, acid anhydrides, etc.
  • Examples thereof include a polyol, or a mixture of a polyester polyol obtained by a dehydration condensation reaction of the aromatic dicarboxylic acid, its acid ester, acid anhydride and the like with a polyol, and another polyester polyol.
  • polyester polyols examples include polyester polyols obtained by dehydration condensation reaction of non-aromatic dicarboxylic acids, their acid esters, acid anhydrides and the like with polyols, and ⁇ Rataton-based polyester polyols obtained by ring-opening polymerization of cyclic ester (ie, latatane) monomers such as prolatatatone, alkyl-substituted ⁇ -force prolatatone, ⁇ -valerolataton, alkyl-substituted ⁇ -valerolataton, and the like.
  • cyclic ester ie, latatane
  • polyester polyols obtained by a dehydration condensation reaction of the aromatic dicarboxylic acid, its acid ester, acid anhydride, etc. with non-aromatic dicarboxylic acid, their acid ester, acid anhydride, etc. and polyol are preferred. .
  • polyol examples include ethylene glycol, 1,3-propylene glycol, 1,2_propylene glycol, 1,4-butylene glycol, 1,5_pentandaricone, 1,6-hexane glycol, 3_Methyl_1,5_Pentandalycol, 2_Butyl_2—Ethyl_1,3_Propanediol, Neopentylglycol, 1,8_Octaneglycol, 1,9-Nonanediol, Diethylene glycol, Cyclohexane 1, 1,4-dio mononole, cyclohexane _ 1, 4_ dimethanol, dimer acid dinore, trimethylololepropane, glycerin, hexanetriol, or glycols such as ethylene oxide or propylene oxide adducts thereof And triol.
  • the aromatic ring has an acid component (specifically, the aromatic dicarboxylic acid, its acid ester, and acid anhydrate). Etc.), preferably introduced from.
  • the polyester polyol does not contain an aromatic ring in the molecule, and specifically includes, for example, dicarboxylic acids other than the above-mentioned aromatics, their acid esters, acid anhydrides and the like (aromatics Polyester polyol obtained by a dehydration condensation reaction with a polyol (other than the above), and a rataton-based polyester polyol obtained by ring-opening polymerization of the cyclic ester (ie, rataton) monomer.
  • polyester polyols obtained by a dehydration condensation reaction of the above-mentioned non-aromatic dicarboxylic acids, their acid esters, acid anhydrides and the like with polyols (other than aromatic) are preferred.
  • polyester polyols are preferably viscous liquids at room temperature.
  • the molecular weights of these (A) and (B) polyester polyols are preferably 200 to 20,000 S, particularly those having a molecular weight of 400 to 10,000. If the molecular weight is too large, the introduction amount of urethane groups or the like is decreased, and the toughness of the polyurethane resin is not preferable because the strength and cohesive force are decreased. If the molecular weight is too small, the polyurethane resin tends to be brittle, which is preferable.
  • Examples of (C) dimethylolalkanoic acid include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, dimethylolhexanoic acid, dimethylolheptanoic acid, dimethyloloctanoic acid, dimethylolnonanoic acid, and dimethylolnonanoic acid. Methyloldecanoic acid is mentioned.
  • dimethylol butanoic acid is preferred.
  • Examples of the organic polyisocyanate (D) include organic polyisocyanate compounds containing modified organic polyisocyanate in addition to organic polyisocyanate monomers.
  • aliphatic diisocyanates and / or alicyclic diisocyanates are preferred, and alicyclic diisocyanates are preferred.
  • the number average molecular weight of the resulting polyurethane tree is f 3,000 to 60,000, in particular 10,000 to 40,000.
  • any apparatus may be used as long as the above reaction can be achieved.
  • examples thereof include a mixing and kneading apparatus such as a reaction kettle or kneader equipped with a stirring apparatus, a uniaxial or multiaxial extrusion reactor, and the like.
  • a metal catalyst such as dibutyltin dilaurate or a tertiary amine catalyst such as triethylamine can be used.
  • silane coupling agent in the base resin solution for example, I - methacryloxy propyl Le trimethoxysilane, and Byurushiran compounds such Bulle triethoxysilane, beta - (3, epoxysilane compounds such Tokishishiran and, I - ⁇ Examples include minopropyltriethoxysilane, compounds, and mercaptosilane compounds such as ⁇ -mercaptopropyltrimethoxysilane.
  • ⁇ -glycidoxypropyltrimethoxysilane is preferred, with epoxysilane compounds being preferred.
  • the compounding amount of the silane coupling agent is 0.05 to 10.00 parts by mass with respect to 100 parts by mass of the solid content of the polyurethane resin, from the viewpoints of the base material film covering area of the coupling agent and the coating efficiency and adhesive performance. Further, it is preferably 0.1 to 5.00 parts by mass.
  • organic solvent in the main agent solution examples include inert organic solvents commonly used in the polyurethane industry, for example, aromatic hydrocarbon solvents such as toluene and xylene, ester-based homogeneous 1J such as ethyl acetate and butyl acetate, Ketone solvents such as methyl ethyl ketone and cyclohexanone, glycol ether ester solvents such as ethylene glycol eno retinoate acetate, propylene glycol eno methenoate acetate, ethyl _ 3 _ ethoxypropionate, tetrahydrofuran, Examples include ether solvents such as dioxane, and polar solvents such as dimethylenolenolemamide, dimethylacetamide, N_methylpyrrolidone, and furfural. These can be used alone or in admixture of two or more.
  • aromatic hydrocarbon solvents such as toluene and xy
  • the compound described above as (D) organic polyisocyanate can be used.
  • Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd.
  • Organic polyisocyanate modified products such as Coronate 3041, Coronate HL, and Coronate HX are preferred.
  • the compounding amount of the isocyanate curing agent is preferably from! To 30 parts by mass, particularly from 3 to 15 parts by mass in terms of solids per 100 parts by mass of the solid content of the polyurethane resin.
  • a catalyst, a foam stabilizer and the like can be used in combination. These can be blended in the isocyanate curing agent, but are preferably blended in the main agent solution.
  • the catalyst specifically, for example, dibutyltin dilaurate, di O lipped rutin dill Ureto, tin catalysts such as stannous O transfected benzoate, triethylene di ⁇ Min, Toryechiruamin, N, N, N r, N r - tetra methyl propylene diene ⁇ Min, N, N, N r, N r - tetrakis (2-hydroxypropyl Honoré) Echirenjiamin, N- methylmorpholine, 1, 2-Jimechiruimida tetrazole, 1, 5-Jiaza one bicyclo (4, 3, 0) Nonene 1, 5, 8—Diazabicyclo (5, 4, 0) —undecene 1 (DBU), borane salts
  • Amine salt catalysts magnesium naphthenate, lead naphthenate, potassium acetate and other carboxylates, triethylphosphine, tribenzylphosphine and other trialkylphosphines, Alkoxides such as potassium methylate, zinc-based organometallic catalysts.
  • the blending amount of the catalyst is preferably 0.001 to 5.00% by mass, particularly 0.01 to 2.00% by mass with respect to the solid content of the polyurethane resin.
  • Examples of the foam stabilizer include at least one reaction with a polyglycol ether containing a necessary number of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, preferably ethylene oxide.
  • a polyglycol ether containing a necessary number of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, preferably ethylene oxide.
  • Such organic compounds containing at least one reactive hydrogen atom include alcohols, phenols, thiols, primary or secondary amines, carboxylic acids or sulfonic acids, and nonionic surfactants that are amides thereof. Examples include 1J and polyalkylene oxide derivatives of phenolic compounds having one or more alkyl group substituents.
  • pull nick type surfactants which are 1, 2 _, such as butylene oxide, butylene oxide, phenylethylene oxide, cyclohexene oxide, propylene oxide, or mixtures thereof.
  • the alkylene oxide or substituted alkylene oxide is polymerized in the presence of an alkali catalyst to give the corresponding water-insoluble polyalkylene group. It is a nonionic surfactant obtained by producing recall and condensing with the required number of moles of ethylene oxide under the same conditions.
  • alcohols obtained by reducing aldehydes produced by catalytic reaction of polyolefins such as tripropylene, tetrapropylene, pentapropylene, ditributylene, triisobutylene, propyleneisobutylene and tributene with carbon monoxide and hydrogen.
  • polyolefins such as tripropylene, tetrapropylene, pentapropylene, ditributylene, triisobutylene, propyleneisobutylene and tributene with carbon monoxide and hydrogen.
  • nonionic surfactants obtained by reacting ethylene oxide in the number of moles.
  • organic polysiloxane can also be mentioned as an example of a preferable foam stabilizer.
  • the blending amount of the foam stabilizer is preferably 3% by mass or less based on the solid content of the polyurethane resin.
  • Films used for laminating in the present invention include metal foils such as Al and Cu, stretched polypropylene, unstretched polypropylene (hereinafter abbreviated as CPP), polyester (hereinafter abbreviated as PET), and nylon.
  • CPP unstretched polypropylene
  • PET polyester
  • nylon nylon
  • LLDPE linear low density polyethylene
  • low density polyethylene high density polyethylene
  • ethylene vinyl acetate copolymer polyvinyl alcohol
  • ethylene vinyl alcohol copolymer examples thereof include plastic films such as polystyrene, polycarbonate, polyvinylidene chloride, and polyvinyl chloride, paper, and films obtained by polymer coating on these.
  • These films are preferably subjected to an appropriate surface treatment such as a corona discharge treatment before lamination in order to improve the adhesive force.
  • the adhesive for laminating of the present invention can be used in a known laminating method such as dry lamination, hot-melt lamination, and ethanol extrusion lamination.
  • the laminated film can complete the curing reaction by aging at room temperature (preferably 40 to 50 ° C) for a certain time (preferably within 48 hours).
  • a reactor equipped with a stirrer, thermometer, nitrogen seal tube and cooler was charged with 25 g of ethylene glycol and 400 g of talented pentinoreglinole. After melting at 120 ° C, 269 g of didipic acid and isophthalic acid were added. 306 g of acid was charged and esterification was performed at 220 ° C under normal pressure. After flowing out the prescribed water, add 0.03 g of tetrabutyl titanate, gradually reduce the pressure from normal pressure to 2.7 kPa abs (absolute pressure) over 5 hours, and conduct transesterification at 220 ° C for 5 hours. A polyester polyol having an acid value of 0.4 mgK0H / g, a hydroxyl value of 56. lmgK0H / g, a number average molecular weight of 2,000, and a room temperature viscous liquid was obtained.
  • This polyester polyol is referred to as A_1.
  • This polyester polyol is referred to as A-2.
  • Polyester polyol monole A-1, A-2, and dimethylolbutanoic acid were dissolved in ethyl acetate, and a catalyst (dioctyltin dilaurate) was added thereto.
  • a catalyst dioctyltin dilaurate
  • isophorone Diisocyanate was added and reacted to produce a polyurethane resin solution having a nonvolatile content of 80% by mass.
  • the adhesives of Examples 1 to 7 or Comparative Examples 1 to 4 were applied to the first plastic film and dried, and then the second plastic film or metal foil was applied to the first plastic film with a nip roll. Bonding and aging were performed to produce a two-layer laminate film. In addition, using this two-layer laminate film, the adhesive was further applied and dried, and then the third plastic film was bonded with a nip roll and aged to produce a three-layer laminated film. .
  • Adhesive solid content 30% (diluted with ethyl acetate)
  • Laminate film composition 15 ⁇ / 60 ⁇ LLDPE
  • Adhesive application amount 3.5 g / m 2 (after drying)
  • Polyester polyol A-1 506.2 475.2 475.2 475.2 475.2 455.5 402.4
  • Adipic acid / isofuric acid / ethylene glycol / neopentyl glycol 269/306/25/400
  • Adipic acid / ethylene glycol / diethylene glycol 61 1/148/241
  • the film configuration for retort is PETZA1 / CPP, from the standpoint of not causing problems such as the occurrence of broken bags when dropped and the occurrence of peeling during long-term storage,
  • the adhesive strength must be at least 5.0 N / I 5 mm.
  • An adhesive for laminating was produced by the following steps, and appearance evaluation immediately after the retort treatment was performed by the same methods as in Examples:! -7 and Comparative Examples 1-4.
  • An esterification reaction was carried out at 180 to 220 ° C. under nitrogen flow using 548.5 g of isophthalanolic acid and 839.2 g of diethyleneglycolole.
  • 482.5 g of adipic acid was added and an esterification reaction was carried out at 180 to 220 ° C. to obtain a polyester polyol XA having a number average molecular weight of about 2,000.
  • the whole amount was dissolved in 400. Og of ethyl acetate to obtain a solution having a solid content of 80%.
  • the esterification reaction was carried out at 180 to 220 ° C. under a nitrogen stream using 529.4 g of isophthalenolic acid, 128.8 g of ethylene glycol and 302.4 g of talented pentinoregulinole.
  • 214.8 g of sebacic acid was added, and esterification was performed at 180 to 220 ° C. to obtain a polyester polyol XB having a number average molecular weight of about 3,000. .
  • the whole amount was dissolved in 428.6 g of ethyl acetate to obtain a solution having a solid content of 70%.
  • Stanotato tin-based urethanization catalyst: produced by Yoshitomi Fine Chemical Co., Ltd.
  • the mixture was cooled to 70 ° C., and 330.07 g of ethyl acetate was added to obtain a polyurethane resin solution XC having a solid content of 50%.
  • the number average molecular weight of the obtained polyurethane resin was about 10,000.
  • polyester polyol X having a number average molecular weight of about 5,500.
  • polyester polyol XD containing a carboxyl group was obtained which had a dissolution angle of 600.96 g of oxalate ethinole and made a solution with a solid content of 50%.
  • about 2 mol% of the terminal hydroxyl groups were reacted with trimellitic anhydride.
  • the retort treatment was performed in the same manner as in Examples:! To 7 and Comparative Examples:! To 4, and the appearance immediately after the treatment was confirmed. As a result, peeling was confirmed.
  • the laminate film produced using the laminating adhesive of the present invention can be widely used for food packaging, refill container packaging and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Disclosed is an adhesive for laminates which has high initial adhesion, high productivity and good workability while maintaining excellent resistance to contents. Specifically disclosed is an adhesive for laminates composed of a base material solution and an isocyanate curing agent. The base material solution contains at least a polyurethane resin, a silane coupling agent and an organic solvent, and the polyurethane resin is obtained by reacting the following components (A), (B), (C) and (D) at a mass ratio of (A)/(B)=95/5-75/25 (A) a polyester polyol containing an aromatic ring in a molecule wherein a hydroxyl group substantially forms a molecular end (B) a polyester polyol containing no aromatic ring in a molecule (C) a dimethylolalkanoic acid (D) an organic polyisocyanate

Description

明 細 書  Specification
ラミネート用接着剤  Laminating adhesive
技術分野  Technical field
[0001] 本発明は、特に金属などのフィルムのドライラミネートに好適な接着剤に関する。  [0001] The present invention relates to an adhesive particularly suitable for dry lamination of a film of metal or the like.
背景技術  Background art
[0002] 最近、包装方法として、その強度、商品保護性、包装時の作業適性、包装による宣 伝効果、プラスチック材料の大量、安価な供給による包装コストの低減等の理由から 、複合フレキシブルパッケージングが著しく発展してきてレ、る。  [0002] Recently, as a packaging method, composite flexible packaging due to its strength, product protection, workability at the time of packaging, transmission effect by packaging, large amount of plastic material, reduction of packaging cost by cheap supply, etc. Has developed significantly.
このようなフィルムのラミネートに用いられる接着剤としては、接着性能や耐寒、耐 熱性に優れている点、各種プラスチック、金属箔等の基材への適応範囲の広さ等か ら、一般には、水酸基等の活性水素基を有する主剤とイソシァネート基を有する硬化 剤からなる二液型ポリウレタン系接着剤が主流となっている。  As an adhesive used for laminating such a film, in general, it has excellent adhesion performance, cold resistance, and heat resistance, and has a wide range of application to substrates such as various plastics and metal foils. Two-component polyurethane adhesives consisting of a main agent having an active hydrogen group such as a hydroxyl group and a curing agent having an isocyanate group have become mainstream.
しかし、現在の二液型ポリウレタン系ラミネート用接着剤は、接着後の接着剤の硬 化反応が非常におそいため、いわゆるエージングと称する硬化促進工程を必要とす る。具体的にいえば、ラミネート加工したフィルムを 35〜60°Cの保温室にて 3〜5日 間程度保管してエージングすることにより接着剤を硬化させることが必要となってくる 。この際、エージング条件によって接着剤の硬化の度合いが変ってくるため、ラミネー トフイルムの接着強度に影響を及ぼすことがあり、エージングが不十分な場合には、 接着剤の硬化不良によるデラミネーシヨン (層剥離)を引き起こすことがある。特に脂 肪族ポリウレタン系接着剤では、この硬化反応にかなり長時間を要する。したがって、 このようなエージング工程は、ドライラミネーシヨンプロセスにおレ、て不可欠の工程で あり、エージング用の保温室設置のための設備投資およびその後の保温のためのュ 一ティリティー等の費用が必要であった。  However, the current two-component polyurethane laminate adhesive requires a curing acceleration process called aging because the curing reaction of the adhesive after bonding is very slow. Specifically, it is necessary to cure the adhesive by storing and aging the laminated film in a 35-60 ° C storage room for about 3-5 days. At this time, since the degree of curing of the adhesive varies depending on the aging conditions, it may affect the adhesive strength of the laminating film. If the aging is insufficient, delamination due to poor curing of the adhesive ( May cause delamination. Particularly in the case of an aliphatic polyurethane adhesive, this curing reaction takes a considerably long time. Therefore, such an aging process is an indispensable process in the dry lamination process, and there is an expense such as capital investment for the installation of a greenhouse for aging and utility for the subsequent heat insulation. It was necessary.
[0003] これらの点を解決して、養生時間の短縮化ひいては生産効率の向上や、塗工、接 着性能を改善するため、特許文献 1では、（a)ジエチレングリコール系ポリエステルポ リウレタンポリオールと（b)カルボキシル基含有芳香族系ポリエステルポリオールと（c )ポリイソシァネートを含有するドライラミネート用接着剤が提案されている。この（b)力 ルボキシル基含有芳香族系ポリエステルポリオールは、ポリエステルポリオールに無 水芳香族多価カルボン酸を反応させて得られるものであるため、ポリエステルポリオ ールの分子末端がカルボキシル基となっている。その結果、特許文献 1のドライラミネ ート用接着剤を用いて製造したラミネートフィルム包装材料は、内容物として食品や 医薬品等を充填してボイル、レトルト等の高温処理を行なう用途に使用したときの接 着性能、耐熱水性、耐酸性などの耐内容物性能を向上させることができたが、フィノレ ムの高温処理後の外観（剥離）はむしろ著しく悪化している。 [0003] In order to solve these points and shorten the curing time, thereby improving the production efficiency and improving the coating and adhesion performance, Patent Document 1 describes (a) diethylene glycol-based polyester polyol polyol and ( There has been proposed an adhesive for dry laminate containing b) a carboxyl group-containing aromatic polyester polyol and (c) a polyisocyanate. This (b) force Since a ruboxyl group-containing aromatic polyester polyol is obtained by reacting a polyester polyol with a water-free aromatic polyvalent carboxylic acid, the molecular end of the polyester polyol is a carboxyl group. As a result, the laminated film packaging material manufactured using the dry laminate adhesive disclosed in Patent Document 1 is filled with food or pharmaceuticals as the contents and used for high temperature processing such as boiling and retort. Although the content performance such as adhesion performance, hot water resistance, and acid resistance could be improved, the appearance (peeling) of finoleum after high temperature treatment was rather deteriorated.
特許文献 1：特開 2000— 154365号公報  Patent Document 1: Japanese Unexamined Patent Publication No. 2000-154365
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0004] 本発明は、優れた耐内容物性能を維持しつつ、初期接着性が高ぐ生産性、作業 性も良好なラミネート用接着剤を提供することを目的とする。 [0004] An object of the present invention is to provide an adhesive for laminating with excellent productivity and workability with high initial adhesiveness while maintaining excellent content resistance performance.
課題を解決するための手段  Means for solving the problem
[0005] 本発明者らは、主剤の主要構成成分であるポリウレタン樹脂の原料として、 （A)分 子中に芳香環を含有する剛直ポリエステルポリオールと（B)それ以外の柔軟ポリエス テルポリオールを併用し、かつ、樹脂中の特定部位にカルボキシル基を導入すること により、前記課題を解決しうることを見いだし、本発明を完成するに至った。  [0005] The inventors of the present invention use (A) a rigid polyester polyol containing an aromatic ring in the molecule and (B) another flexible polyester polyol as a raw material for a polyurethane resin that is a main component of the main agent. In addition, the present inventors have found that the above problem can be solved by introducing a carboxyl group at a specific site in the resin, and have completed the present invention.
すなわち、本発明は次の（1)〜（3)である。  That is, the present invention includes the following (1) to (3).
[0006] (1) 少なくとも、以下の (A)と（B)と（C)と（D)とを質量比 (A) Z (B) = 95Z5〜75 Z25で反応させて得られるポリウレタン樹脂、シランカップリング剤及び有機溶剤を 含有する主剤溶液と、イソシァネート硬化剤とからなること、を特徴とするラミネート用 接着剤。  (1) A polyurethane resin obtained by reacting at least the following (A), (B), (C) and (D) at a mass ratio (A) Z (B) = 95Z5 to 75Z25, A laminating adhesive comprising: a main agent solution containing a silane coupling agent and an organic solvent; and an isocyanate curing agent.
(A)分子中に芳香環を含有し且つ分子末端が実質的に水酸基であるポリエステノレ ポリオ一ノレ  (A) Polyesterol having an aromatic ring in the molecule and having substantially a hydroxyl group at the molecular end
(B)分子中に芳香環を含有しなレ、ポリエステルポリオール  (B) A polyester polyol that does not contain an aromatic ring in the molecule
(C)ジメチロールアルカン酸  (C) Dimethylolalkanoic acid
(D)有機ポリイソシァネート  (D) Organic polyisocyanate
[0007] (2) (A)と（B)の双方が常温で粘稠な液体である、前記（1)のラミネート用接着剤。 [0008] (3) (C)がジメチロールブタン酸である、前記（1)又は（2)のラミネート用接着剤。 発明の効果 [0007] (2) The laminating adhesive according to (1), wherein both (A) and (B) are viscous liquids at room temperature. [0008] (3) The adhesive for laminating according to (1) or (2), wherein (C) is dimethylolbutanoic acid. The invention's effect
[0009] 本発明のラミネート用接着剤を使用して製造したプラスチックフィルムや金属箔など のラミネートフィルムは、優れた耐内容物性能を維持しつつ、初期剥離接着強度や 常態剥離接着強度などの接着性能も優れている。また、煮沸処理やレトルト処理後も ラミネートフィルムの外観にデラミネーシヨン等の異常はみられず、実用的な接着強 度を保持していることが確認された。その結果、フィルム製造の際に、トンネリングゃ フィルムのズレを防止することでき、生産性、作業性も良好となった。  [0009] Laminate films such as plastic films and metal foils produced using the laminating adhesive of the present invention have excellent peel resistance and adhesion such as initial peel adhesive strength and normal peel adhesive strength. The performance is also excellent. In addition, it was confirmed that there was no abnormality such as delamination in the appearance of the laminate film after boiling or retort treatment, and that it maintained practical adhesive strength. As a result, in film production, tunneling can prevent the film from shifting, and the productivity and workability are also improved.
したがって、本発明により、ラミネートフィルムの生産性や作業性が大幅に向上し、 コストダウンや短納期化が可能となった。  Therefore, according to the present invention, the productivity and workability of the laminate film are greatly improved, and the cost can be reduced and the delivery time can be shortened.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0010] 以下、本発明について詳しく説明する。 [0010] Hereinafter, the present invention will be described in detail.
本発明のラミネート用接着剤は、少なくとも主剤溶液とイソシァネート硬化剤とから なる。  The laminating adhesive of the present invention comprises at least a main agent solution and an isocyanate curing agent.
本発明における主剤溶液は、ポリウレタン樹脂、シランカップリング剤及び有機溶剤 を含有する。  The main agent solution in the present invention contains a polyurethane resin, a silane coupling agent, and an organic solvent.
主剤溶液におけるポリウレタン樹脂は、（A)分子中に芳香環を含有し且つ分子末 端が実質的に水酸基であるポリエステルポリオールと（B)分子中に芳香環を含有し なレ、ポリエステルポリオールと（C)ジメチロールアルカン酸と（D)有機ポリイソシァネ 一トとを反応させて得られるものである。  The polyurethane resin in the main agent solution comprises (A) a polyester polyol having an aromatic ring in the molecule and a molecular end substantially having a hydroxyl group, and (B) a polyester polyol having no aromatic ring in the molecule, polyester polyol ( It is obtained by reacting C) dimethylolalkanoic acid with (D) organic polyisocyanate.
更に、（A)分子中に芳香環を含有し且つ分子末端が実質的に水酸基であるポリェ ステルポリオールと（B)分子中に芳香環を含有しないポリエステルポリオールの質量 比（A) / (B)は、 95/5〜75/25である。  Further, (A) Mass ratio of polyester polyol having an aromatic ring in the molecule and a molecular terminal substantially having a hydroxyl group and (B) polyester polyol not having an aromatic ring in the molecule (A) / (B) Is from 95/5 to 75/25.
[0011] (A)ポリエステルポリオールは、分子中に芳香環を含有しているが、分子末端が実 質的に水酸基である（すなわち、分子末端には実質的にカルボキシル基が存在しな レ、）。具体的には、ポリエステルポリオールの酸価が lmgK〇H/g以下であることが 好ましい。 [0011] (A) Polyester polyol contains an aromatic ring in the molecule, but the molecular terminal is substantially a hydroxyl group (that is, a carboxyl group does not substantially exist at the molecular terminal, ). Specifically, the acid value of the polyester polyol is preferably 1 mgK0H / g or less.
(A)ポリエステルポリオールとしては、具体的には例えば、テレフタル酸、イソフタノレ 酸などの芳香族ジカルボン酸、その酸エステル、酸無水物等とポリオールとの脱水縮 合反応で得られるポリエステルポリオール、或いは、前記芳香族ジカルボン酸、その 酸エステル、酸無水物等とコハク酸、アジピン酸、セバシン酸、ァゼライン酸、へキサ ヒドロテレフタル酸、へキサヒドロイソフタル酸等の芳香族以外のジカルボン酸、それ らの酸エステル、酸無水物等とポリオールとの脱水縮合反応で得られるポリエステル ポリオール、或いは、前記芳香族ジカルボン酸、その酸エステル、酸無水物等とポリ オールとの脱水縮合反応で得られるポリエステルポリオールと、これ以外のポリエステ ルポリオールとの混合物が挙げられる。このような（これ以外の）ポリエステルポリオ一 ルとしては、芳香族以外のジカルボン酸、それらの酸エステル、酸無水物等とポリオ ールとの脱水縮合反応で得られるポリエステルポリオールや、 ε一力プロラタトン、ァ ルキル置換 ε —力プロラタトン、 δ—バレロラタトン、アルキル置換 δ—バレロラタトン 等の環状エステル (すなわちラタトン)モノマーの開環重合により得られるラタトン系の ポリエステルポリオールなどが挙げられる。 Specific examples of (A) polyester polyols include terephthalic acid and isophthalanol. A polyester polyol obtained by a dehydration condensation reaction of an aromatic dicarboxylic acid such as an acid, its acid ester, an acid anhydride, and the like with a polyol, or the aromatic dicarboxylic acid, its acid ester, an acid anhydride, etc., and a succinic acid, Polyester obtained by dehydration condensation reaction of non-aromatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, acid esters, acid anhydrides, etc. Examples thereof include a polyol, or a mixture of a polyester polyol obtained by a dehydration condensation reaction of the aromatic dicarboxylic acid, its acid ester, acid anhydride and the like with a polyol, and another polyester polyol. Examples of such polyester polyols (other than this) include polyester polyols obtained by dehydration condensation reaction of non-aromatic dicarboxylic acids, their acid esters, acid anhydrides and the like with polyols, and ε Rataton-based polyester polyols obtained by ring-opening polymerization of cyclic ester (ie, latatane) monomers such as prolatatatone, alkyl-substituted ε-force prolatatone, δ-valerolataton, alkyl-substituted δ-valerolataton, and the like.
これらのうち、前記芳香族ジカルボン酸、その酸エステル、酸無水物等と芳香族以 外のジカルボン酸、それらの酸エステル、酸無水物等とポリオールとの脱水縮合反応 で得られるポリエステルポリオールが好ましい。  Of these, polyester polyols obtained by a dehydration condensation reaction of the aromatic dicarboxylic acid, its acid ester, acid anhydride, etc. with non-aromatic dicarboxylic acid, their acid ester, acid anhydride, etc. and polyol are preferred. .
前記ポリオールとしては、例えば、エチレングリコール、 1, 3—プロピレングリコール 、 1， 2_プロピレングリコーノレ、 1， 4—ブチレングリコーノレ、 1， 5 _ペンタンダリコーノレ 、 1， 6—へキサングリコール、 3 _メチル _ 1， 5 _ペンタンダリコール、 2_ブチル _ 2 —ェチル _ 1， 3 _プロパンジオール、ネオペンチルグリコール、 1， 8_オクタングリ コール、 1 , 9—ノナンジオール、ジエチレングリコール、シクロへキサン一1 , 4—ジォ 一ノレ、シクロへキサン _ 1， 4_ジメタノーノレ、ダイマー酸ジォーノレ、 トリメチローノレプロ パン、グリセリン、へキサントリオール、或いはこれらのエチレンオキサイドまたはプロ ピレンオキサイド付加物等のグリコールやトリオールが挙げられる。  Examples of the polyol include ethylene glycol, 1,3-propylene glycol, 1,2_propylene glycol, 1,4-butylene glycol, 1,5_pentandaricone, 1,6-hexane glycol, 3_Methyl_1,5_Pentandalycol, 2_Butyl_2—Ethyl_1,3_Propanediol, Neopentylglycol, 1,8_Octaneglycol, 1,9-Nonanediol, Diethylene glycol, Cyclohexane 1, 1,4-dio mononole, cyclohexane _ 1, 4_ dimethanol, dimer acid dinore, trimethylololepropane, glycerin, hexanetriol, or glycols such as ethylene oxide or propylene oxide adducts thereof And triol.
これらはいずれも単独で或いは 2種以上を混合して使用することができる。  Any of these may be used alone or in admixture of two or more.
なお、入手のし易さ（安価であり、且つ一般的に工業生産されている等）から、芳香 環については酸成分 (具体的には前記芳香族ジカルボン酸、その酸エステル、酸無 水物等）から導入されることが好ましレ、。 [0012] (B)ポリエステルポリオールは、分子中に芳香環を含有しないものであり、具体的に は例えば、前記の芳香族以外のジカルボン酸、それらの酸エステル、酸無水物等と（ 芳香族以外の）ポリオールとの脱水縮合反応で得られるポリエステルポリオールや、 前記の環状エステル (すなわちラタトン)モノマーの開環重合により得られるラタトン系 のポリエステルポリオールが挙げられる。 It should be noted that because of availability (inexpensive and generally industrially produced, etc.), the aromatic ring has an acid component (specifically, the aromatic dicarboxylic acid, its acid ester, and acid anhydrate). Etc.), preferably introduced from. [0012] (B) The polyester polyol does not contain an aromatic ring in the molecule, and specifically includes, for example, dicarboxylic acids other than the above-mentioned aromatics, their acid esters, acid anhydrides and the like (aromatics Polyester polyol obtained by a dehydration condensation reaction with a polyol (other than the above), and a rataton-based polyester polyol obtained by ring-opening polymerization of the cyclic ester (ie, rataton) monomer.
これらは単独で或いは 2種以上を混合して使用することができる。  These can be used alone or in admixture of two or more.
これらのうち、前記の芳香族以外のジカルボン酸、それらの酸エステル、酸無水物 等と（芳香族以外の）ポリオールとの脱水縮合反応で得られるポリエステルポリオール が好ましい。  Of these, polyester polyols obtained by a dehydration condensation reaction of the above-mentioned non-aromatic dicarboxylic acids, their acid esters, acid anhydrides and the like with polyols (other than aromatic) are preferred.
[0013] これらの（A) (B)ポリエステルポリオールはいずれも常温で粘稠液体であるのが好 ましい。  [0013] All of these (A) and (B) polyester polyols are preferably viscous liquids at room temperature.
また、これら（A) (B)ポリエステルポリオールの分子量はいずれも 200〜20, 000力 S 好ましぐ特に、分子量 400〜10, 000のものが好ましい。分子量が大きすぎると、ゥ レタン基等の導入量が減少して、ポリウレタン樹脂の強靭性ゃ強レ、凝集力が減少し 好ましくない。分子量が小さすぎると、ポリウレタン樹脂が脆くなる傾向があり好ましく なレ、。  The molecular weights of these (A) and (B) polyester polyols are preferably 200 to 20,000 S, particularly those having a molecular weight of 400 to 10,000. If the molecular weight is too large, the introduction amount of urethane groups or the like is decreased, and the toughness of the polyurethane resin is not preferable because the strength and cohesive force are decreased. If the molecular weight is too small, the polyurethane resin tends to be brittle, which is preferable.
[0014] (C)ジメチロールアルカン酸としては、例えば、ジメチロールプロピオン酸、ジメチ口 ールブタン酸、ジメチロールペンタン酸、ジメチロールへキサン酸、ジメチロールヘプ タン酸、ジメチロールオクタン酸、ジメチロールノナン酸、ジメチロールデカン酸が挙 げられる。  [0014] Examples of (C) dimethylolalkanoic acid include dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, dimethylolhexanoic acid, dimethylolheptanoic acid, dimethyloloctanoic acid, dimethylolnonanoic acid, and dimethylolnonanoic acid. Methyloldecanoic acid is mentioned.
これらは単独で或いは 2種以上を混合して使用することができる。  These can be used alone or in admixture of two or more.
このうち、ジメチロールブタン酸が好ましい。  Of these, dimethylol butanoic acid is preferred.
[0015] (D)有機ポリイソシァネートとしては、有機ポリイソシァネートモノマーの他に、有機 ポリイソシァネートの変性体を含む有機ポリイソシァネートイ匕合物などが挙げられる。 例えば、 2, 4_トリレンジイソシァネート、 2, 6 _トリレンジイソシァネート、キシレン _ 1， 4—ジイソシァネート、キシレン一1 , 3—ジイソシァネート、 4, 一ジフエ二ノレ メタンジイソシァネート、 2, 4; —ジフエニルメタンジイソシァネート、 4, 一ジフエ ニルエーテルジイソシァネート、 2—二トロジフエ二ルー 4, Α' ージイソシァネート、 2 ， 2' —ジフエニルプロパン一 4, 4' —ジイソシァネート、 3， 3' —ジメチルジフエ二 ノレメタン一 4， 一ジイソシァネート、 4, 一ジフエニルプロパンジイソシァネート、 m—フエ二レンジイソシァネート、 p—フエ二レンジイソシァネート、ナフチレン一 1， 4 —ジイソシァネート、ナフチレン一 1 , 5—ジイソシァネート、 3, 3; —ジメトキシジフエ ニル一4, A' —ジイソシァネート等の芳香族ジイソシァネート、テトラメチレンジィソシ ァネート、へキサメチレンジイソシァネート、リジンジイソシァネート等の脂肪族ジイソ シァネート、イソホロンジイソシァネート、水素添加トリレンジイソシァネート、水素添加 キシレンジイソシァネート、水素添加ジフエニルメタンジイソシァネート、テトラメチルキ シレンジイソシァネート等の脂環族ジイソシァネート等のジイソシァネート、および前 記ジイソシァネートのビウレット体、ダイマー体、トリマー体、ダイマー'トリマー体、ウレ トンイミン変性体などのポリメリック体や、 2官能以上のポリオール等と前記のジイソシ ァネート或いはそのポリメリック体との反応で得られるポリイソシァネートのァダクト体 などの有機ポリイソシァネート変性体が挙げられる。 [0015] Examples of the organic polyisocyanate (D) include organic polyisocyanate compounds containing modified organic polyisocyanate in addition to organic polyisocyanate monomers. For example, 2,4_tolylene diisocyanate, 2,6_tolylene diisocyanate, xylene_1,4-diisocyanate, xylene-1,3-diisocyanate, 4,1-diphenole methane diisocyanate, 2, 4 ; —Diphenylmethane diisocyanate, 4, 1-diphenyl ether diisocyanate, 2—2-diphenyl ether di-isocyanate, 2 , 2 '-diphenylpropane-1,4,4'-diisocyanate, 3,3 '-dimethyldiphenylmethane 4,4,1 diisocyanate, 4,1 diphenylpropanediisocyanate, m-phenylene diisocyanate, p —Phenylene diisocyanate, naphthylene-1,4—Diisocyanate, naphthylene-1,5, diisocyanate, 3, 3 ; —Dimethoxydiphenyl-1,4, A ′ —Diisocyanate and other aromatic diisocyanates, tetramethylene dissociates Aliphatic diisocyanates such as cyanate, hexamethylene diisocyanate and lysine diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane Fats such as isocyanate and tetramethyl xylene diisocyanate Diisocyanates such as polyisocyanate diisocyanates, and polymer forms such as biuret, dimer, trimer, dimer 'trimer, and uretonimine modified forms of the above diisocyanates, and bifunctional or higher functional polyols, and the above diisocynates or their polymeric forms. And organic polyisocyanate modified products such as adducts of polyisocyanate obtained by the reaction with.
これらは単独で或いは 2種以上を混合して使用することができる。  These can be used alone or in admixture of two or more.
これらのうち、脂肪族ジイソシァネート及び/又は脂環族ジイソシァネート、更に脂 環族ジイソシァネートが好ましレ、。  Of these, aliphatic diisocyanates and / or alicyclic diisocyanates are preferred, and alicyclic diisocyanates are preferred.
主剤溶液におけるポリウレタン樹脂は、（A)分子中に芳香環を含有し且つ分子末 端が実質的に水酸基であるポリエステルポリオールと（B)分子中に芳香環を含有し なレ、ポリエステルポリオールと（C)ジメチロールアルカン酸と（D)有機ポリイソシァネ ートとを（八）/ (8) = 95 5〜75/25 (質量比）で、好ましくは、イソシァネート基の 当量 Z水酸基の当量 = 0. 50/1. 00〜0. 98/1. 00、 100°C以下で各成分を均 一に混合し反応させて製造することができる。  The polyurethane resin in the main agent solution comprises (A) a polyester polyol having an aromatic ring in the molecule and a molecular end substantially having a hydroxyl group, and (B) a polyester polyol having no aromatic ring in the molecule, polyester polyol ( C) Dimethylolalkanoic acid and (D) organic polyisocyanate at (8) / (8) = 95 5 to 75/25 (mass ratio), preferably equivalent of isocyanate group equivalent of Z hydroxyl group = 0. Each component can be mixed and reacted uniformly at 50 / 1.00 to 0.98 / 1.00, 100 ° C or less.
得られるポリウレタン樹月旨の数平均分子量 fま 3, 000〜60， 000、特に 10， 000〜4 0， 000であること力 子ましレヽ。  The number average molecular weight of the resulting polyurethane tree is f 3,000 to 60,000, in particular 10,000 to 40,000.
反応装置としては、上記の反応が達成できればレ、かなる装置でも良ぐ例えば、攪 拌装置の付いた反応釜やニーダー、一軸または多軸押し出し反応機等の混合混練 装置が挙げられる。  As the reaction apparatus, any apparatus may be used as long as the above reaction can be achieved. Examples thereof include a mixing and kneading apparatus such as a reaction kettle or kneader equipped with a stirring apparatus, a uniaxial or multiaxial extrusion reactor, and the like.
反応を早く進めるため、触媒として、ポリウレタンゃポリウレアの製造において常用さ れるジブチル錫ジラウレート等の金属触媒ゃトリエチルァミン等の三級アミン触媒を 用レ、ることちできる。 Used as a catalyst in the production of polyurethane-polyurea as a catalyst to accelerate the reaction. A metal catalyst such as dibutyltin dilaurate or a tertiary amine catalyst such as triethylamine can be used.
[0017] 主剤溶液におけるシランカップリング剤としては、例えば、 Ί—メタクリロキシプロピ ルトリメトキシシラン、ビュルトリエトキシシランなどのビュルシラン化合物や、 β - (3， トキシシランなどのエポキシシラン化合物や、 Ί—ァミノプロピルトリエトキシシラン、 Ν 合物や、 γ —メルカプトプロピルトリメトキシシランなどのメルカプトシラン化合物が挙 げられる。 [0017] As the silane coupling agent in the base resin solution, for example, I - methacryloxy propyl Le trimethoxysilane, and Byurushiran compounds such Bulle triethoxysilane, beta - (3, epoxysilane compounds such Tokishishiran and, I - § Examples include minopropyltriethoxysilane, compounds, and mercaptosilane compounds such as γ-mercaptopropyltrimethoxysilane.
これらは単独で或いは 2種以上を混合して使用することができる。  These can be used alone or in admixture of two or more.
これらのうち、エポキシシラン化合物が好ましぐ γーグリシドキシプロピルトリメトキ シシランがより好ましい。  Of these, γ-glycidoxypropyltrimethoxysilane is preferred, with epoxysilane compounds being preferred.
シランカップリング剤の配合量は、カップリング剤の基材フィルム被覆面積と被覆効 率および接着性能等の点から、ポリウレタン樹脂の固形分 100質量部に対して 0. 05 〜10. 00質量部、さらに 0. 1〜5. 00質量部であることが好ましい。  The compounding amount of the silane coupling agent is 0.05 to 10.00 parts by mass with respect to 100 parts by mass of the solid content of the polyurethane resin, from the viewpoints of the base material film covering area of the coupling agent and the coating efficiency and adhesive performance. Further, it is preferably 0.1 to 5.00 parts by mass.
[0018] 主剤溶液における有機溶剤としては、ポリウレタン工業において常用の不活性な有 機溶剤、例えば、トルエン、キシレン等の芳香族炭化水素系溶剤、酢酸ェチル、酢酸 ブチル等のエステル系溶斉 1J、メチルェチルケトン、シクロへキサノン等のケトン系溶剤 、エチレングリコーノレエチノレエーテノレアセテート、プロピレングリコーノレメチノレエーテ ルアセテート、ェチル _ 3 _エトキシプロピオネート等のグリコールエーテルエステル 系溶剤、テトラヒドロフラン、ジォキサン等のエーテル系溶剤、ジメチノレホノレムアミド、 ジメチルァセトアミド、 N_メチルピロリドン、フルフラール等の極性溶剤が挙げられる これらは単独で或いは 2種以上を混合して使用することができる。 [0018] Examples of the organic solvent in the main agent solution include inert organic solvents commonly used in the polyurethane industry, for example, aromatic hydrocarbon solvents such as toluene and xylene, ester-based homogeneous 1J such as ethyl acetate and butyl acetate, Ketone solvents such as methyl ethyl ketone and cyclohexanone, glycol ether ester solvents such as ethylene glycol eno retinoate acetate, propylene glycol eno methenoate acetate, ethyl _ 3 _ ethoxypropionate, tetrahydrofuran, Examples include ether solvents such as dioxane, and polar solvents such as dimethylenolenolemamide, dimethylacetamide, N_methylpyrrolidone, and furfural. These can be used alone or in admixture of two or more.
[0019] 本発明におけるイソシァネート硬化剤としては、（D)有機ポリイソシァネートとして前 述した化合物などを使用することができるが、具体的には、 日本ポリウレタン工業 (株 )製のコロネート L、コロネート 3041、コロネート HL、コロネート HX等の有機ポリイソ シァネート変性体が好適である。 イソシァネート硬化剤の配合量は、ポリウレタン樹脂の固形分 100質量部に対して 固形分換算で:!〜 30質量部、特に 3〜： 15質量部が好ましい。 [0019] As the isocyanate curing agent in the present invention, the compound described above as (D) organic polyisocyanate can be used. Specifically, Coronate L manufactured by Nippon Polyurethane Industry Co., Ltd., Organic polyisocyanate modified products such as Coronate 3041, Coronate HL, and Coronate HX are preferred. The compounding amount of the isocyanate curing agent is preferably from! To 30 parts by mass, particularly from 3 to 15 parts by mass in terms of solids per 100 parts by mass of the solid content of the polyurethane resin.
[0020] 本発明においては、更に触媒や整泡剤などを併用することができる。これらはイソシ ァネート硬化剤に配合することも可能であるが、主剤溶液に配合するのが好ましい。 触媒としては、具体的には例えば、ジブチルチンジラウレート、ジォクチルチンジラ ゥレート、スタナスォクトエート等の錫系触媒、トリエチレンジァミン、トリェチルァミン、 N, N, Nr , Nr —テトラメチルプロピレンジァミン、 N， N, Nr , Nr —テトラキス（2 ーヒドロキシプロピノレ）エチレンジァミン、 N—メチルモルホリン、 1 , 2—ジメチルイミダ ゾール、 1 , 5—ジァザ一ビシクロ（4, 3, 0)ノネン一 5、 1 , 8—ジァザビシクロ（5, 4, 0)—ゥンデセン一 7 (DBU)、これらアミン系触媒のボラン塩、 DBUフエノール塩、 D BUォクチル酸塩、 DBU炭酸塩等の各種アミン塩系触媒、ナフテン酸マグネシウム、 ナフテン酸鉛、酢酸カリウムなどのカルボキシレート類、トリェチルホスフィン、トリベン ジルホスフィン等のトリアルキルホスフィン類、ナトリウムメチラートなどのアルコキシド 類、亜鉛系有機金属触媒が挙げられる。 In the present invention, a catalyst, a foam stabilizer and the like can be used in combination. These can be blended in the isocyanate curing agent, but are preferably blended in the main agent solution. As the catalyst, specifically, for example, dibutyltin dilaurate, di O lipped rutin dill Ureto, tin catalysts such as stannous O transfected benzoate, triethylene di § Min, Toryechiruamin, N, N, N r, N r - tetra methyl propylene diene § Min, N, N, N r, N r - tetrakis (2-hydroxypropyl Honoré) Echirenjiamin, N- methylmorpholine, 1, 2-Jimechiruimida tetrazole, 1, 5-Jiaza one bicyclo (4, 3, 0) Nonene 1, 5, 8—Diazabicyclo (5, 4, 0) —undecene 1 (DBU), borane salts of these amine catalysts, DBU phenol salts, D BU octylates, DBU carbonates, etc. Amine salt catalysts, magnesium naphthenate, lead naphthenate, potassium acetate and other carboxylates, triethylphosphine, tribenzylphosphine and other trialkylphosphines, Alkoxides such as potassium methylate, zinc-based organometallic catalysts.
触媒の配合量は、ポリウレタン樹脂の固形分に対して 0. 001 -5. 00質量％、特に 0. 01 -2. 00質量％が望ましい。  The blending amount of the catalyst is preferably 0.001 to 5.00% by mass, particularly 0.01 to 2.00% by mass with respect to the solid content of the polyurethane resin.
[0021] 整泡剤としては、例えば、エチレンォキシド、プロピレンォキシド、ブチレンォキシド 、好ましくはエチレンォキシド、のようなアルキレンォキシドの必要な数を含有するポリ グリコールエーテルと、少なくとも 1個の反応性水素原子を含有する有機化合物とを 縮合することによって得られるもの力挙げられる。このような少なくとも 1個の反応性水 素原子を含有する有機化合物としては、アルコール、フエノーノレ、チオール、第一又 は第二アミン、カルボン酸又はスルホン酸、それらのアミドである非イオン性界面活性 斉 1J、また、 1個以上のアルキル基換基を有するフヱノール系化合物のポリアルキレン ォキシド誘導体等が挙げられる。 [0021] Examples of the foam stabilizer include at least one reaction with a polyglycol ether containing a necessary number of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, preferably ethylene oxide. The strength obtained by condensing with an organic compound containing a reactive hydrogen atom. Such organic compounds containing at least one reactive hydrogen atom include alcohols, phenols, thiols, primary or secondary amines, carboxylic acids or sulfonic acids, and nonionic surfactants that are amides thereof. Examples include 1J and polyalkylene oxide derivatives of phenolic compounds having one or more alkyl group substituents.
また、プル口ニック型界面活性剤を挙げることができ、これは、ブチレンォキシド、了 ミレンォキシド、フエニルエチレンォキシド、シクロへキセンォキシド、プロピレンォキシ ド、又はそれらの混合物のような、 1 , 2 _アルキレンォキシド又は置換アルキレンォキ シドをアルカリ触媒の存在下で重合させて、対応する水に不溶性のポリアルキレング リコールを製造し、同条件下でエチレンォキシドの必要なモル数と縮合して得られる 非イオン性界面活性剤である。 There may also be mentioned pull nick type surfactants, which are 1, 2 _, such as butylene oxide, butylene oxide, phenylethylene oxide, cyclohexene oxide, propylene oxide, or mixtures thereof. The alkylene oxide or substituted alkylene oxide is polymerized in the presence of an alkali catalyst to give the corresponding water-insoluble polyalkylene group. It is a nonionic surfactant obtained by producing recall and condensing with the required number of moles of ethylene oxide under the same conditions.
更に、トリプロピレン、テトラプロピレン、ペンタプロピレン、ジトリブチレン、トリイソブ チレン、プロピレンイソブチレン及びトリブテン等のようなポリオレフインと一酸化炭素 及び水素との触媒反応によって生成するアルデヒドを還元して得られるアルコールに 、必要なモル数のエチレンォキシドを反応させて得られる非イオン性界面活性剤等 が挙げられる。  Furthermore, it is necessary for alcohols obtained by reducing aldehydes produced by catalytic reaction of polyolefins such as tripropylene, tetrapropylene, pentapropylene, ditributylene, triisobutylene, propyleneisobutylene and tributene with carbon monoxide and hydrogen. Examples thereof include nonionic surfactants obtained by reacting ethylene oxide in the number of moles.
また更に、有機ポリシロキサンも好ましい整泡剤の一例として挙げることができる。 整泡剤の配合量は、ポリウレタン樹脂の固形分に対して 3質量％以下が好ましい。  Furthermore, organic polysiloxane can also be mentioned as an example of a preferable foam stabilizer. The blending amount of the foam stabilizer is preferably 3% by mass or less based on the solid content of the polyurethane resin.
[0022] 本発明においてラミネートするのに用いるフィルムとしては、 Al、 Cuなどの金属箔、 延伸ポリプロピレン、無延伸ポリプロピレン（以下 CPPと略称する。）、ポリエステル（以 下 PETと略称する。）、ナイロン (以下 NYと略称する。）、直鎖状低密度ポリエチレン（ 以下 LLDPEと略称する。）、低密度ポリエチレン、高密度ポリエチレン、エチレン 酢酸ビニル共重合体、ポリビエルアルコール、エチレン ビニルアルコール共重合 体、ポリスチレン、ポリカーボネート、ポリ塩化ビニリデン、ポリ塩化ビニルなどのプラス チックフィルム、紙等、およびこれらにポリマーコーティングを施したフィルムが挙げら れる。 [0022] Films used for laminating in the present invention include metal foils such as Al and Cu, stretched polypropylene, unstretched polypropylene (hereinafter abbreviated as CPP), polyester (hereinafter abbreviated as PET), and nylon. (Hereinafter abbreviated as NY), linear low density polyethylene (hereinafter abbreviated as LLDPE), low density polyethylene, high density polyethylene, ethylene vinyl acetate copolymer, polyvinyl alcohol, ethylene vinyl alcohol copolymer, Examples thereof include plastic films such as polystyrene, polycarbonate, polyvinylidene chloride, and polyvinyl chloride, paper, and films obtained by polymer coating on these.
これらのフィルムは、ラミネートを行う前にコロナ放電処理などの適切な表面処理を 行うことが接着力を向上させるうえで好ましい。  These films are preferably subjected to an appropriate surface treatment such as a corona discharge treatment before lamination in order to improve the adhesive force.
また、ポリマーコートフィルムは、気泡発生、接着力低下等の問題が発生する可能 性があるため、コーティングされているポリマーの種類、コーティング量、表面特性等 を事前に考慮しておく必要がある。  In addition, since polymer coated films may cause problems such as bubble generation and reduced adhesive strength, it is necessary to consider the type of coated polymer, coating amount, surface characteristics, etc. in advance.
[0023] 本発明のラミネート用接着剤は、ドライラミネーシヨン、ホットメルトラミネーシヨン、ェ タストルージョンラミネーシヨン等公知のラミネート方法にて用いることが可能である。 そしてラミネートされたフィルムは、常温 (好ましくは 40〜50°C)下で一定時間（好まし くは 48時間以内）のエージングで硬化反応を完了することが可能である。 [0023] The adhesive for laminating of the present invention can be used in a known laminating method such as dry lamination, hot-melt lamination, and ethanol extrusion lamination. The laminated film can complete the curing reaction by aging at room temperature (preferably 40 to 50 ° C) for a certain time (preferably within 48 hours).
このような本発明により、 2枚のフィルムがラミネートされたフィルムだけでな 3枚 以上のフィルムがラミネートされたものも製造することができる。 実施例 According to the present invention, it is possible to manufacture a film in which three or more films are laminated only by a film in which two films are laminated. Example
[0024] 次に、本発明の実施例について詳細に説明する力 本発明はこれら実施例により 限定して解釈されるものではない。特にことわりのない限り、合成例、実施例及び比 較例中の％は「質量％」を意味する。  Next, the power to explain the embodiments of the present invention in detail The present invention is not construed as being limited to these embodiments. Unless otherwise specified,% in Synthesis Examples, Examples and Comparative Examples means “% by mass”.
[0025] 〔分子中に芳香環を含有し且つ分子末端が実質的に水酸基であるポリエステルポリ オールの合成〕 [Synthesis of polyester polyol having an aromatic ring in the molecule and a molecular terminal substantially having a hydroxyl group]
'  '
攪拌機、温度計、窒素シール管および冷却器のついた反応器に、エチレングリコ 一ノレ 25gと才ヽ才ペンチノレグリ ーノレ 400gを仕込み、 120°Cにて溶角军後、了ジピン酸 2 69gとイソフタル酸 306gを仕込み、常圧下 220°Cでエステル化反応を行った。所定 の水を流出後、テトラブチルチタネート 0. 03gを加え、 5時間かけて常圧より 2. 7kPa abs (絶対圧）まで徐々に減圧した後、 220°Cで 5時間エステル交換反応を行レ、、酸 価 0. 4mgK〇H/g、水酸基価 56. lmgK〇H/g、数平均分子量 2, 000、常温粘 稠液体のポリエステルポリオールを得た。  A reactor equipped with a stirrer, thermometer, nitrogen seal tube and cooler was charged with 25 g of ethylene glycol and 400 g of talented pentinoreglinole. After melting at 120 ° C, 269 g of didipic acid and isophthalic acid were added. 306 g of acid was charged and esterification was performed at 220 ° C under normal pressure. After flowing out the prescribed water, add 0.03 g of tetrabutyl titanate, gradually reduce the pressure from normal pressure to 2.7 kPa abs (absolute pressure) over 5 hours, and conduct transesterification at 220 ° C for 5 hours. A polyester polyol having an acid value of 0.4 mgK0H / g, a hydroxyl value of 56. lmgK0H / g, a number average molecular weight of 2,000, and a room temperature viscous liquid was obtained.
このポリエステルポリオールを A_ 1と称する。  This polyester polyol is referred to as A_1.
[0026] 〔分子中に芳香環を含有しなレ、ポリエステルポリオールの合成〕 [Synthesis of a polyester polyol containing no aromatic ring in the molecule]
合成例 2  Synthesis example 2
合成例 1と同様の反応器に、エチレングリコール 148gとジエチレングリコール 148g を仕込み、 120°Cにて溶解後、アジピン酸 61 lgを仕込み、常圧下 220°Cでエステル 化反応を行った。所定の水を流出後、テトラブチルチタネート 0. 03gを加え、 5時間 力けて常圧より 2. 7kPa abs (絶対圧）まで徐々に減圧した後、 220°Cで 5時間エス テル交換反応を行い、酸価 0. 3mgKOH/g、水酸基価 56. lmgKOH/g、数平 均分子量 2, 000、常温粘稠液体のポリエステルポリオールを得た。  In the same reactor as in Synthesis Example 1, 148 g of ethylene glycol and 148 g of diethylene glycol were charged, dissolved at 120 ° C, 61 lg of adipic acid was charged, and esterification was performed at 220 ° C under normal pressure. After flowing out the prescribed water, add 0.03 g of tetrabutyl titanate, gradually reduce the pressure from normal pressure to 2.7 kPa abs (absolute pressure) by applying 5 hours, and then perform ester exchange reaction at 220 ° C for 5 hours. Thus, a polyester polyol having an acid value of 0.3 mgKOH / g, a hydroxyl value of 56. lmgKOH / g, a number average molecular weight of 2,000, and a room temperature viscous liquid was obtained.
このポリエステルポリオールを A— 2と称する。  This polyester polyol is referred to as A-2.
[0027] 実施例 1〜 7および比較例：!〜 4 [0027] Examples 1 to 7 and comparative examples:! To 4
〔ポリウレタン樹脂の合成〕  [Synthesis of polyurethane resin]
ポリエステルポリオ一ノレ A— 1、 A— 2、及びジメチロールブタン酸を酢酸ェチルに 溶解し、これに触媒 (ジォクチルチンジラウレート）を加えた。この中に更にイソホロン ジイソシァネートを加えて反応させて、不揮発分 80質量％のポリウレタン樹脂溶液を 製造した。 Polyester polyol monole A-1, A-2, and dimethylolbutanoic acid were dissolved in ethyl acetate, and a catalyst (dioctyltin dilaurate) was added thereto. In addition to this, isophorone Diisocyanate was added and reacted to produce a polyurethane resin solution having a nonvolatile content of 80% by mass.
〔主剤溶液の調製〕  (Preparation of main agent solution)
得られた該ポリウレタン樹脂溶液に、酢酸ェチル、シランカップリング剤（信越化学 工業（株)製 KBM _403、 —グリシドキシプロピルトリメトキシシラン）と消泡剤（ビッ タケミー 'ジャパン社製 BYK— 354)を配合して、不揮発分 60質量％のラミネート用 接着剤の主剤溶液を調製した。  To the obtained polyurethane resin solution, ethyl acetate, a silane coupling agent (KBM _403 manufactured by Shin-Etsu Chemical Co., Ltd., —glycidoxypropyltrimethoxysilane) and an antifoaming agent (BITK Chemy's BYK manufactured by Japan) ) To prepare a main agent solution of an adhesive for laminating having a nonvolatile content of 60% by mass.
〔ラミネート用接着剤の調製〕  [Preparation of adhesive for laminating]
調製した該主剤溶液とイソシァネート硬化剤（日本ポリウレタン工業 (株)製コロネ一 ト HX、へキサメチレンジイソシァネートのトリマー体、イソシァネート基含有量 21 · 3 % 、固形分 100%)を用いて、下記方法によりラミネートフィルムを製造し、その性能を 試験した。  Using the prepared main agent solution and isocyanate curing agent (Nihon Polyurethane Industry Co., Ltd. Coronet HX, hexamethylene diisocyanate trimer, isocyanate group content 21 · 3%, solid content 100%) A laminate film was produced by the following method and its performance was tested.
これらの結果をまとめて表 1に示す。  These results are summarized in Table 1.
[0028] 〔ラミネートフィルムの製造〕 [Manufacture of laminate film]
以下に示す条件で、実施例 1〜7又は比較例 1〜4の接着剤を第 1のプラスチックフ イルムに塗布し乾燥させた後、これに第 2のプラスチックフィルムまたは金属箔をニッ プロールにてはりあわせ、エージングして、 2層ラミネートフィルムを製造した。また、こ の 2層ラミネートフィルムを用いて、これに更に前記接着剤を塗布し乾燥させた後、第 3のプラスチックフィルムをニップロールにてはりあわせ、エージングして、 3層ラミネ一 トフイルムを製造した。  Under the conditions shown below, the adhesives of Examples 1 to 7 or Comparative Examples 1 to 4 were applied to the first plastic film and dried, and then the second plastic film or metal foil was applied to the first plastic film with a nip roll. Bonding and aging were performed to produce a two-layer laminate film. In addition, using this two-layer laminate film, the adhesive was further applied and dried, and then the third plastic film was bonded with a nip roll and aged to produce a three-layer laminated film. .
接着剤の固形分 ： 30% (酢酸ェチルによる希釈）  Adhesive solid content: 30% (diluted with ethyl acetate)
ラミネートフィルムの構成： 15 μ ΝΥ/60 μ LLDPE  Laminate film composition: 15 μΝΥ / 60 μ LLDPE
12 μ PET/7 μ Al/70 μ CPP  12 μPET / 7 μ Al / 70 μ CPP
接着剤の塗布量 ：3. 5g/m2 (乾燥後） Adhesive application amount: 3.5 g / m 2 (after drying)
乾燥条件 ： 80°C X 5秒間  Drying conditions: 80 ° C x 5 seconds
エージング条件 ： 40°C X 30時間  Aging condition: 40 ° C x 30 hours
[0029] 〔ラミネートフィルムの性能試験〕  [Performance test of laminate film]
以下に示す条件でラミネートフィルムの評価を行った。結果をまとめて表 1に示す。 初期剥離接着強度： 25°Cで張り合わせた直後に T型剥離試験 The laminate film was evaluated under the following conditions. The results are summarized in Table 1. Initial peel adhesion strength: T-type peel test immediately after bonding at 25 ° C
(JIS K 6854に準拠）  (Compliant with JIS K 6854)
§ I張速度： 300mm/min  § I tension speed: 300mm / min
常態剥離接着強度：張り合わせた後 40°Cで 30時間経過したのちに T型剥離試験  Normal peel adhesion strength: T-type peel test after 30 hours at 40 ° C after bonding
(JIS K 6854に準拠）  (Compliant with JIS K 6854)
§ I張速度： 300mm/min  § I tension speed: 300mm / min
耐内容物性（レトルト処理）： PET/ A1ZCPPからなるラミネートフィルムを 4  Content resistance (retort treatment): 4 laminated films of PET / A1ZCPP
0°C X 30時間エージング処理した直後にヒートシール してバウチを作成し、食酢/食用油/トマトケチャップ = 1/1/1 (質量比）の混合物を充填後、 135°C X 30分間で蒸気レトルト処理を行なレ、、 A1/CPP間 の剥離接着強度を測定した。  Heat seal immediately after aging treatment at 0 ° CX for 30 hours to create a bouch and fill with a mixture of vinegar / edible oil / tomato ketchup = 1/1/1 (mass ratio), then steam retort at 135 ° C for 30 minutes After the treatment, the peel adhesion strength between A1 / CPP was measured.
耐内容物性（ボイル処理）： NY/LLDPE力 なるラミネートフィルムを 40°C X  Content resistance (boiled): NY / LLDPE strength laminate film at 40 ° C X
30時間エージング処理した直後にヒートシールしてパゥ チを作成し、水/食用油 = 1/9 (質量比）の混合物を充 填後、 100°C X 30分間でボイル処理を行ない、 NY/ LLDPE間の剥離接着強度を測定した。  Heat seal immediately after aging treatment for 30 hours to make a pouch, and after filling with water / edible oil = 1/9 (mass ratio), boil at 100 ° C for 30 minutes, NY / LLDPE The peel adhesion strength between them was measured.
[表 1] [table 1]
実 施 例 Example
1 2 3 4 5 6 7 ポリウレタン樹脂製造原料 （g) ,)  1 2 3 4 5 6 7 Raw material for polyurethane resin production (g),)
ポリエステルポリオール A— 1 ?) 506.2 475.2 475.2 475.2 475.2 455.5 402.4 Polyester polyol A-1 ) 506.2 475.2 475.2 475.2 475.2 455.5 402.4
A- 2 30.6 61.1 61.1 61.1 61.1 80.4 133.6 主 ジメチロールブタン酸 5.0 5.0 5.0 5.0 5.0 5.0 5.0 ィソホロンジィソシァネート 56.8 56.8 56.8 56.8 56.8 56.8 56.8 剤  A- 2 30.6 61.1 61.1 61.1 61.1 80.4 133.6 Major dimethylolbutanoic acid 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Isophorone disocyanate 56.8 56.8 56.8 56.8 56.8 56.8 56.8
シラン力'ソプリング剤 (g) 2.99 2.99 2.93 2.99 2.99 2.99 2.99 溶  Silane force 'sopling agent (g) 2.99 2.99 2.93 2.99 2.99 2.99 2.99
酢酸ェチル （g) 398.7 398.7 398.7 398.7 398.7 398.7 398.7 液  Ethyl acetate (g) 398.7 398.7 398.7 398.7 398.7 398.7 398.7 Solution
触媒 (g) 0.12 0.12 0.12 0.12 0.12 消泡剤 (g) 0.02 0.02 0.02 0.02 0.02 イソシァネー卜硬化剤 （g) 55.6 55.6 55.6 55.6 55.6 55.6 55.6 ポリエステルポリオールの質 MJ:匕  Catalyst (g) 0.12 0.12 0.12 0.12 0.12 Antifoam (g) 0.02 0.02 0.02 0.02 0.02 Isocyanate curing agent (g) 55.6 55.6 55.6 55.6 55.6 55.6 55.6 Polyester polyol quality MJ: J
A- 1/A- 2 94/6 89/11 89/11 89/11 89/11 85/15 75/25 主剤溶液/ィソシァネー卜硬化剤 （質量比） 18/1 18/1 18/1 18/1 18/1 18/1 18/1 ラミネートフィルムの性能  A- 1 / A- 2 94/6 89/11 89/11 89/11 89/11 85/15 75/25 Main agent solution / Isocyanate hardener (mass ratio) 18/1 18/1 18/1 18 / 1 18/1 18/1 18/1 Performance of laminated film
初期剥離接着 ¾Jt (N/1 5mm)  Initial peel adhesion ¾Jt (N / 1 5mm)
A 1/CPP間 0.65 0.75 0.75 0.75 0.75 0.9 1.25 Between A 1 / CPP 0.65 0.75 0.75 0.75 0.75 0.9 1.25
NY/LLDP E間 0.6 0.7 0.7 0.7 0.7 0.85 1.1 常態剥離接着髓 (N/1 5mm) NY / LLDP E 0.6 0.7 0.7 0.7 0.7 0.85 1.1 Normal peel adhesion (N / 1 5mm)
A 1/CPP間 12.3 12.2 12.2 12.2 12.2 11.6 8.4 Between A 1 / CPP 12.3 12.2 12.2 12.2 12.2 11.6 8.4
NY/LLDP E間 材 ¾1 材破 材破 材破 材破 材破 7 耐内容物性 （N/1 5mm) NY / LLDP E material ¾1 Material broken material Broken material Broken material Broken material 7 Content resistance (N / 1 5mm)
1 35°Cレトルト 10 9.8 9.8 9.8 9.8 7.8 5 レトルト処理直後の外観 剥離 剥離 剥離 剥離 剥離 剥離 剥離 なし なし なし なし なし なし なし 1 35 ° C retort 10 9.8 9.8 9.8 9.8 7.8 5 Appearance immediately after retorting Peel Peel Peel Peel Peel Peel Peel Peel None None None None None None None
10 (TCボイル 材破 材破 材破 材破 材破 材破 6 注 1 ) ポリエステルポリオール A— 1 10 (TC boiled material broken material broken material broken material broken material broken 6 Note 1) Polyester polyol A— 1
：アジピン酸/イソフ夕ル酸/エチレングリコール/ネオペンチルグリコール =269/306/25/400  : Adipic acid / isofuric acid / ethylene glycol / neopentyl glycol = 269/306/25/400
2) ポリエステルポリオール A - 2  2) Polyester polyol A-2
：アジピン酸 Zエチレングリコール ジエチレングリコール =6 1 1/148/24 : Adipic acid Z ethylene glycol Diethylene glycol = 6 1 1/148/24
3)材破：材職壊 3) Material breakage: Material job breakage
Figure imgf000015_0001
Figure imgf000015_0001
注 1) ポリエステルポリオール A— 1  Note 1) Polyester polyol A— 1
：アジピン酸/イソフタル酸 /エチレングリコール/ネオペンチルグリコール  Adipic acid / isophthalic acid / ethylene glycol / neopentyl glycol
=269/306/25/400  = 269/306/25/400
2) ポリエステルポリオ一ル A— 2  2) Polyester polyol A— 2
：アジピン酸/エチレングリコール/ジエチレングリコール =61 1/148/241 : Adipic acid / ethylene glycol / diethylene glycol = 61 1/148/241
3)材破：材料破壊 3) Material failure: Material failure
レトルト用のフィルム構成が例えば PETZA1/CPPである場合、落下した際におけ る破袋の発生や、長期保存時における剥離の発生等といったような不具合をおこさ ないことの観点から、レトルト処理後の接着強度としては、少なくとも 5.0N/I5mm 以上が必要である。  For example, if the film configuration for retort is PETZA1 / CPP, from the standpoint of not causing problems such as the occurrence of broken bags when dropped and the occurrence of peeling during long-term storage, The adhesive strength must be at least 5.0 N / I 5 mm.
また、ボイル用のフィルム構成が例えば NY/LLDPである場合においても、レトル ト用と同じ様な観点から、少なくとも同程度の接着強度が必要である。 [0033] 比較例 5 Further, even when the film configuration for the boil is, for example, NY / LLDP, at least the same adhesive strength is required from the same viewpoint as for the retort. [0033] Comparative Example 5
以下に示す工程によりラミネート用接着剤を製造し、実施例:!〜 7並びに比較例 1 〜4と同じ方法により、レトルト処理直後の外観評価を行った。  An adhesive for laminating was produced by the following steps, and appearance evaluation immediately after the retort treatment was performed by the same methods as in Examples:! -7 and Comparative Examples 1-4.
[0034] 〔ポリエステルポリオ一ノレ XAの製造〕  [Manufacture of Polyester Polio Nore XA]
イソフタノレ酸 548. 5g、ジエチレングリコーノレ 839. 2gを用レヽて、窒素気流下 180〜 220°Cでエステル化反応を行なった。次いで、所定量の水を留出後、アジピン酸 48 2. 5gを加え、 180〜220°Cでエステル化反応を行なレ、、数平均分子量約 2， 000の ポリエステルポリオール XAを得た。この全量を酢酸ェチル 400. Ogに溶解し固形分 80%の溶液とした。  An esterification reaction was carried out at 180 to 220 ° C. under nitrogen flow using 548.5 g of isophthalanolic acid and 839.2 g of diethyleneglycolole. Next, after distilling a predetermined amount of water, 482.5 g of adipic acid was added and an esterification reaction was carried out at 180 to 220 ° C. to obtain a polyester polyol XA having a number average molecular weight of about 2,000. The whole amount was dissolved in 400. Og of ethyl acetate to obtain a solution having a solid content of 80%.
[0035] 〔ポリエステルポリオール XBの製造〕  [Production of polyester polyol XB]
イソフタノレ酸 529. 4g、エチレングリ ーノレ 128. 8g、才ヽ才ペンチノレグリ ーノレ 302. 4gを用いて、窒素気流下 180〜220°Cでエステルイ匕反応を行なった。次いで、所定 量の水を留出後、セバシン酸 214. 8gを力 Pえ、 180〜220°Cでエステル化反応を行 なレ、、数平均分子量約 3, 000のポリエステルポリオール XBを得た。この全量を酢酸 ェチル 428. 6gに溶解し固形分 70%の溶液とした。  The esterification reaction was carried out at 180 to 220 ° C. under a nitrogen stream using 529.4 g of isophthalenolic acid, 128.8 g of ethylene glycol and 302.4 g of talented pentinoregulinole. Next, after distilling out a predetermined amount of water, 214.8 g of sebacic acid was added, and esterification was performed at 180 to 220 ° C. to obtain a polyester polyol XB having a number average molecular weight of about 3,000. . The whole amount was dissolved in 428.6 g of ethyl acetate to obtain a solution having a solid content of 70%.
[0036] 〔ポリウレタン樹脂溶液 XCの製造〕  [Manufacture of polyurethane resin solution XC]
ポリエステノレポリ才ーノレ XA160. 74g、ポリエステノレポリ才ーノレ XB459. 26gを窒 素雰囲気下 50°Cで均一に混合後、イソホロンジイソシァネート 49. 83gをカロえ 77〜8 0°Cで 3時間ウレタンィ匕反応を行った。その後、スタノタト (スズ系ウレタン化触媒：吉富 ファインケミカル (株)製） 0. 10gをカ卩えて更に 3時間ウレタン化反応を継続した。ウレ タン化反応終了後、 70°Cまで冷却し、酢酸ェチル 330. 07gをカ卩えて固形分 50%の ポリウレタン樹脂溶液 XCを得た。得られたポリウレタン樹脂の数平均分子量は約 10 ， 000であった。  Polyesterenore Poly-Nore XA 160. 74 g, Polyester Nole Poly-Nore XB459. 26 g in a nitrogen atmosphere, uniformly mixed at 50 ° C, then mixed with isophorone diisocyanate 49. 83 g at 77-80 ° C 3 A time urethane reaction was carried out. Thereafter, Stanotato (tin-based urethanization catalyst: produced by Yoshitomi Fine Chemical Co., Ltd.) was added in an amount of 0.1 g, and the urethanization reaction was continued for another 3 hours. After completion of the urethanization reaction, the mixture was cooled to 70 ° C., and 330.07 g of ethyl acetate was added to obtain a polyurethane resin solution XC having a solid content of 50%. The number average molecular weight of the obtained polyurethane resin was about 10,000.
[0037] 〔ポリエステルポリオ一ノレ XDの製造〕  [0037] [Production of Polyester Polio Nore XD]
イソフタノレ酸 324. 88g、エチレングリ ーノレ 106. 16g、才ヽ才 ンチノレグリ ーノレ 10 2. 61g、 1 , 6—へキサンジォーノレ 151. 34g、醉酸亜 #&0. 20gを用レヽて、室素気流 下 180〜220°Cでエステル化反応を行なった。所定量の水を留出後、アジピン酸 95 . 24gをカロえ、 220〜230oCでエステノレィ匕反応を行なった。徐々に減圧にし 220〜2 30°Cで 60分間反応後、 220〜230°C、：!〜 2Torrで 4時間エステル化反応を行ない 、数平均分子量約 5， 500のポリエステルポリオール Xび を得た。これに無水トリメリ ット酸 0. 96gをカロえ、 140〜150。Cで反応させた後、醉酸ェチノレ 600. 96gに溶角率し 固形分 50%の溶液とした、カルボキシル基を含有するポリエステルポリオール XDを 得た。得られたポリエステルポリオール XDは末端の水酸基の約 2モル％が無水トリメ リット酸と反応したものである。 Isophthalanolic acid 324. 88 g, ethylene greenole 106. 16 g, talented entinogregrinole 10 2. 61 g, 1, 6-hexanediole 151. 34 g, oxalic acid # & 0. The esterification reaction was performed at ~ 220 ° C. After distilling a predetermined amount of water, 95.24 g of adipic acid was prepared and subjected to esterification reaction at 220-230 ° C. Gradually reduce pressure 220-2 After reacting at 30 ° C. for 60 minutes, esterification was carried out at 220 to 230 ° C.:! To 2 Torr for 4 hours to obtain a polyester polyol X having a number average molecular weight of about 5,500. Add 0.96 g of trimellitic anhydride to this, 140-150. After reacting with C, polyester polyol XD containing a carboxyl group was obtained which had a dissolution angle of 600.96 g of oxalate ethinole and made a solution with a solid content of 50%. In the obtained polyester polyol XD, about 2 mol% of the terminal hydroxyl groups were reacted with trimellitic anhydride.
[0038] 〔イソシァネート硬化剤 XEの製造〕  [0038] [Production of isocyanate curing agent XE]
タケネート A— 10 (キシリレンジイソシァネートのトリメチロールプロパン付加体：武田 薬品工業 (株)製） 50gとタケネート A— 40 (イソホロンジイソシァネートのトリメチロー ルプロパン付加体:武田薬品工業 (株)製） 50gとを窒素雰囲気下 50°Cで均一に混 合し、イソシァネート硬化剤 XEを得た。  Takenate A—10 (Trimethylolpropane adduct of xylylene diisocyanate: Takeda Pharmaceutical Co., Ltd.) and 50 g of Takenate A—40 (Trimethylolpropane adduct of isophorone diisocyanate: Takeda Pharmaceutical Co., Ltd.) ) 50 g was uniformly mixed at 50 ° C under a nitrogen atmosphere to obtain isocyanate curing agent XE.
[0039] 〔ラミネート用接着剤の調製及びラミネートフィルムの製造〕  [Preparation of adhesive for lamination and production of laminate film]
ポリウレタン樹脂溶液 XCを 100g、ポリエステルポリオール XDを 100g、イソシァネ ート硬化剤 XEを 23. 5g、及び、シランカップリング剤（信越化学工業 (株)製 KBM— 403)を 0. 5g用いて、実施例：!〜 7並びに比較例:!〜 4と同じ方法により、ラミネートフ イルムを製造した。  Performed using 100 g of polyurethane resin solution XC, 100 g of polyester polyol XD, 23.5 g of isocyanate curing agent XE, and 0.5 g of silane coupling agent (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) Example:! To 7 and Comparative Example:! To 4 A laminate film was produced in the same manner.
[0040] 〔レトルト処理直後の外観評価〕  [0040] [Appearance evaluation immediately after retort processing]
該ラミネートフィルムを用いて、実施例:!〜 7並びに比較例:!〜 4と同じ方法によりレ トルト処理を行い、該処理直後の外観を確認したところ、剥離が確認された。  Using the laminate film, the retort treatment was performed in the same manner as in Examples:! To 7 and Comparative Examples:! To 4, and the appearance immediately after the treatment was confirmed. As a result, peeling was confirmed.
産業上の利用可能性  Industrial applicability
[0041] 本発明のラミネート用接着剤を用いて製造したラミネートフィルムは、食品包装や詰 め替え容器包装などの用途に広く使用することができる。 [0041] The laminate film produced using the laminating adhesive of the present invention can be widely used for food packaging, refill container packaging and the like.

Claims

請求の範囲 The scope of the claims
[1] 少なくとも、以下の (A)と (B)と（C)と (D)とを質量比 (A) / (B) = 95/5〜75/25 で反応させて得られるポリウレタン樹脂、シランカップリング剤及び有機溶剤を含有す る主剤溶液と、イソシァネート硬化剤とからなること、を特徴とするラミネート用接着剤  [1] A polyurethane resin obtained by reacting at least the following (A), (B), (C) and (D) at a mass ratio (A) / (B) = 95/5 to 75/25, A laminating adhesive characterized by comprising a main agent solution containing a silane coupling agent and an organic solvent and an isocyanate curing agent.
(A)分子中に芳香環を含有し且つ分子末端が実質的に水酸基であるポリエステノレ ポリオ一ノレ (A) Polyesterol having an aromatic ring in the molecule and having substantially a hydroxyl group at the molecular end
(B)分子中に芳香環を含有しなレ、ポリエステルポリオール  (B) A polyester polyol that does not contain an aromatic ring in the molecule
(C)ジメチロールアルカン酸  (C) Dimethylolalkanoic acid
(D)有機ポリイソシァネート  (D) Organic polyisocyanate
[2] (A)と (B)の双方が常温で粘稠な液体である、請求項 1に記載のラミネート用接着剤  [2] The laminating adhesive according to claim 1, wherein both (A) and (B) are viscous liquids at room temperature.
[3] (C)がジメチロールブタン酸である、請求項 1又は 2に記載のラミネート用接着剤。 [3] The laminating adhesive according to claim 1 or 2, wherein (C) is dimethylolbutanoic acid.
PCT/JP2006/305107 2005-03-31 2006-03-15 Adhesive for laminate WO2006109395A1 (en)

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JP2005-102310 2005-03-31

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JP2006282768A (en) 2006-10-19
CN101146883B (en) 2012-01-25
JP4771276B2 (en) 2011-09-14
CN101146883A (en) 2008-03-19
KR100918458B1 (en) 2009-09-24
TW200643133A (en) 2006-12-16

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