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
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D65/38—Packaging materials of special type or form
  • B65D65/40—Applications of laminates for particular packaging purposes
• • 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
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
• • 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

Definitions

• the present invention relates to a reactive adhesive, a laminated film using the same, and a package.
• laminates made by laminating various plastic films and laminating plastic films with metal-deposited films and metal foils have been used in various applications, such as packaging materials for foods, pharmaceuticals, and household goods, and barriers. Decoration for roofing materials, roofing materials, solar panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automotive parts, signs, stickers, etc. Used for applications.
• These laminates are appropriately combined with various plastic films, metal-deposited films or metal foils according to the required properties for each application, and an adhesive is selected according to the required properties.
• functions such as strength, resistance to cracking, retort resistance, heat resistance, and content resistance are required to protect the contents from various distribution, storage such as refrigeration, and heat sterilization. Is required.
• a reactive adhesive (also referred to as a two-component adhesive) for reacting a hydroxyl group with an isocyanate
• a reactive adhesive for reacting a hydroxyl group with an isocyanate
• an adhesive comprising a diol compound (A) having two hydroxyl groups and a polyisocyanate (B) having two or more isocyanate groups
• Mn The molecular weight
• the polyisocyanate (B) is a triisocyanate or higher polyisocyanate compound (b1)
• a diisocyanate compound (b2) obtained by adding an isocyanate compound to a polyester diol
• Adhesives that are mixtures of these are known.
• Patent Document 1 It is an adhesive for laminate film of battery packaging materials, and contains polyurethane polyester polyol whose number average molecular weight of polyol component is 5000 or more and less than 14000, and the total content of urethane bond and isocyanate group is specified. It is known that the laminating adhesive within the range of 1 is excellent in molding processability and wet heat resistance (see, for example, Patent Document 2).
• JP 2014-101422 A Japanese Unexamined Patent Publication No. 2016-196580 Japanese Patent Laid-Open No. 2002-3815 JP 2010-248345 A
• the problem to be solved by the present invention can be applied as an adhesive for laminates in which various plastic films, metal vapor deposition films or metal foils are appropriately combined, and has high adhesiveness and lamination even under high-speed coating conditions. It is providing the reactive adhesive which can obtain the laminated
• the present inventors provide a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) comprises polyethylene terephthalate, polyhydric alcohol, and polybasic. It has been found that a reactive adhesive containing a polyester polyol (A1), which is a reaction product obtained by batch charging with an acid, solves the above problems.
• Patent Document 3 discloses a reactivity containing a polyester polyol obtained by decomposing polyethylene terephthalate by a reaction with a low molecular polyol and then a condensation reaction of the decomposed product with a polybasic acid, and a polyisocyanate curing agent.
• An adhesive is disclosed.
• Patent Document 3 has been evaluated for a laminate film prepared by applying an adhesive at a film speed of 50 m / min, there is nothing about a form prepared under high-speed coating conditions at a coating speed of 200 m / min or more. There is no description or suggestion.
• Patent Document 4 discloses that a polyol compound obtained by depolymerizing polyester (a) with polyol (b) having two or more hydroxyl groups in one molecule is used as a raw material for the adhesive.
• the adhesive it has been evaluated for a laminated film which is applied to a film with a film thickness of 30 ⁇ m by an applicator and then laminated, and is prepared under a high speed coating condition of a coating speed of 200 m / min or more.
• a reactive adhesive that uses polyester polyol made from polyethylene terephthalate and has high adhesion and excellent appearance after lamination even under high-speed coating conditions of 200 m / min or more is now available. The fact is not known.
• polyester polyols obtained by the methods disclosed in Patent Documents 3 and 4 cause poor appearance during high-speed coating properties, polyethylene terephthalate, polyhydric alcohol, If the polyester polyol (A1), which is a reaction product obtained by batch charging with a polybasic acid, is used as a component of the reactive adhesive, poor appearance at the time of high-speed coating property hardly occurs, and high after lamination
• the inventors have found that a laminated film having adhesiveness, particularly heat resistance and content resistance, can be obtained, and have reached the present invention.
• the present invention is a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) comprises polyethylene terephthalate, polyhydric alcohol and polybasic acid.
• a reactive adhesive containing a polyester polyol (A1), which is a reaction product obtained by batch charging, is provided.
• the present invention also provides a laminated film obtained by laminating an adhesive layer between a first plastic film and a second plastic film, wherein the adhesive layer is the reaction according to any one of claims 1 to 4.
• a laminated film that is a layer of an adhesive.
• the present invention also provides a package formed by forming the above-described laminated film into a bag shape.
• the present invention provides a method for producing a polyester polyol (A1), in which polyethylene terephthalate, polyhydric alcohol, and polybasic acid are charged and reacted together.
• the present invention also provides a method for producing a polyester polyol (A1) in which polyethylene terephthalate, polyhydric alcohol, and polybasic acid are charged and reacted together and a polyester polyurethane polyol (A2) in which polyisocyanate is reacted.
• the reactive adhesive of the present invention can be applied as an adhesive for laminates in which various plastic films, metal vapor deposited films, or metal foils are appropriately combined, and has high adhesiveness and after lamination even under high-speed coating conditions.
• a laminated film having an excellent appearance can be obtained. Furthermore, since it is excellent in heat resistance and content resistance, it can be suitably used particularly as a food packaging bag.
• the present invention is a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) comprises polyethylene terephthalate, a polyhydric alcohol, a polybasic acid,
• the polyester polyol (A1) which is a reaction product obtained by batch charging, is contained.
• polyester polyol (A) The polyester polyol (A1) contained in the polyol composition (A) is a reaction product obtained by batch preparation of polyethylene terephthalate, polyhydric alcohol, and polybasic acid.
• PET Polyethylene terephthalate used in the present invention
• PET is obtained by polycondensation of terephthalic acid or dimethyl terephthalate and ethylene glycol, and, if necessary, isophthalic acid, phthalic anhydride, adipic acid, Those modified with substances such as cyclohexanedicarboxylic acid, 1,3-butanediol, and cyclohexanedimethanol can also be used.
• commercially available unused PET bottles, PET films, and other products obtained by pulverizing remaining products at the time of production of PET products, recycled PET recovered from waste and washed can be used. Among these, it is preferable to use recycled PET. These can be washed and pelletized from the market.
• the intrinsic viscosity (IV) of PET is preferably 0.50-0.80 dL / g. By being in this range, the polycondensation reaction between PET and other raw materials can be performed at 250 ° C. or lower. This range is also preferable from the viewpoints of the adhesive strength, durability, and heat resistance of the reactive adhesive containing the PET-containing polyester polyol.
• the polyhydric alcohol used by this invention is not specifically limited, A well-known polyhydric alcohol can be used.
• bisphenol A 2,2-bis (4-hydroxyphenyl) propane
• bisphenol B 2,2-bis (4-hydroxyphenyl) butane
• bisphenol F bis (4- Hydroxyphenyl) methane
• bisphenol S bisphenol such as bis (4-hydroxyphenyl) sulfone
• Modification obtained by ring-opening polymerization of the aliphatic polyol and various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether Polyether polyols; Lactone-based polyester polyols obtained by polycondensation reaction of the aliphatic polyols with various lactones such as ⁇ -caprolactone; Bisphenols such as bisphenol A, bisphenol F, and bisphenol S; Bisphenol A, bisphenol F, etc. And an ethylene oxide adduct of bisphenol obtained by adding ethylene oxide to bisphenol.
• various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl gly
• ethylene glycol diethylene glycol, 1,3-propanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neo Preferred are aliphatic polyols such as pentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol, 6-hexanediol is preferred.
• the polybasic acid used by this invention is not specifically limited, A well-known polybasic acid can be used.
• aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid; malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, hexahydro Aliphatic dicarboxylic acids such as phthalic acid and 1,4-cyclohexanedicarboxylic acid; maleic acid, maleic anhydride, citraconic acid, dimethylmaleic acid, cyclopentene-1,2-dicarboxylic acid, 1-cyclohexene-1,2- Aliphatic unsaturated dicarboxylic acids such as dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, fumaric acid, mesaconic acid, itaconic acid, glutaconic acid
• the production method in which PET, polyhydric alcohol, and polybasic acid are charged and reacted together can be arbitrarily produced by a known polycondensation reaction method.
• PET, polyhydric alcohol, and polybasic are available. Acid is added to the production equipment and heated to 180 ° C or higher with stirring in a nitrogen atmosphere, and any production method such as atmospheric pressure dehydration reaction, reduced pressure and vacuum dehydration reaction, solution polycondensation method, solid phase polycondensation reaction, etc. You may carry out in.
• the vacuum dehydration reaction can be applied at a reaction temperature of 230 ° C. or lower, and the reaction time can be set to about 5 hours.
• the progress of the polycondensation reaction can be confirmed by measuring the acid value, hydroxyl value, viscosity or softening point.
• a batch production apparatus such as a reaction vessel equipped with a nitrogen inlet, a thermometer, a stirrer, a rectifying tower, etc. can be suitably used, and a deaeration port is provided. Extruders, continuous reactors, kneaders and the like can also be used.
• the esterification reaction can be promoted by using an esterification catalyst (such as a tin compound, a titanium compound, or a zirconium compound) as necessary.
• the polyol obtained by the method of transesterifying PET in polyhydric alcohol and the method of polycondensation of the transesterification product and polybasic acid decomposes the ethylene terephthalate unit apart. Even if it is used as an agent, the appearance, adhesive strength, heat resistance and content resistance properties during high-speed coating, which are the purposes of the present application, cannot be achieved.
• the polyester polyol (A1) is preferably a polyester polyol using 1,6-hexanediol as the polyhydric alcohol and dimer acid as the polybasic acid.
• the weight fraction of 1,6-hexanediol is preferably from 5 to 20% by mass, more preferably from 6 to 18% by mass as a proportion of the polyester polyol (A1) in the charged raw material.
• the weight fraction of the dimer acid is preferably 5 to 20% by mass, more preferably 6 to 18% by mass, as a proportion of the polyester polyol (A1) in the charged raw material.
• the ratio of the polyester polyol (A1) charged to the total amount of the polyhydric alcohol and polybasic acid is 5 to 50% by mass with respect to 100% of the total amount of polyhydric alcohol and polybasic acid. And more preferably 8 to 48% by mass.
• a long-chain unsaturated dibasic acid such as dimer acid, 1,6-hexanediol, and other monomers are synthesized together with PET, so that the adhesive strength to the substrate is increased.
• the molecular weight body remains as it is, and it is presumed that this contributes to the appearance, adhesive strength, heat resistance and content resistance at high speed coating.
• the polyhydric alcohol is preferably a dihydric alcohol such as 1,6-hexanediol.
• the polyester polyol (A1) preferably has an acid value of 5.0 or less from the viewpoint of hydrolysis resistance, and more preferably 3.0 or less from the viewpoint of the reactivity of the adhesive. Moreover, it is preferable that a hydroxyl value is 50 or less from a viewpoint of high-speed coating property, and 40 or less is more preferable.
• the acid value and the hydroxyl value are measured by the following methods, and indicate values converted into solid contents unless otherwise specified.
• the point showing a slight red color lasting 30 seconds is set as the end point, and the hydroxyl value is calculated by the following formula from the titration amount (V) at that time.
• a blank test is performed at the same time, and the titer at that time is (B).
• the titer of the 0.5 mol / L potassium hydroxide alcohol solution is defined as (F).
• the number average molecular weight of the polyester polyol (A1) is not particularly limited, but is usually adjusted in the range of 2000 to 12000, more preferably 3000 to 8000, from the viewpoint of an appropriate resin viscosity at the time of coating. .
• the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured by gel permeation chromatography (GPC) under the following conditions.
• Measuring device HLC-8220GPC manufactured by Tosoh Corporation Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation + Tosoh Corporation TSK-GEL SuperHZM-M ⁇ 4 Detector: RI (differential refractometer)
• Data processing Multi-station GPC-8020model II manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 0.35 ml / min Standard; Monodisperse polystyrene Sample; Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 ⁇ l)
• polyester polyurethane polyol (A2) The polyester polyol (A1) is a polyester polyurethane polyol (A2) obtained by reacting polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid all at once, and then further reacting with an isocyanate compound described later. Also good. At this time, the isocyanate compound is preferably isophorone diisocyanate.
• the polyester polyurethane polyol (A2) preferably has an acid value of 5.0 or less from the viewpoint of hydrolysis resistance, and more preferably 3.0 or less from the viewpoint of adhesive reactivity. Further, from the viewpoint of heat resistance and content resistance, the hydroxyl value is preferably 30 or less, and more preferably 25 or less.
• polyester polyol (A1) in addition to the polyester polyol (A1), the polyhydric alcohol itself, a polyester polyol that does not use polyethylene terephthalate as a raw material, a polyether polyol, a polyurethane polyol, and a polyether
• a polymer polyol selected from ester polyols, polyester (polyurethane) polyols, polyether (polyurethane) polyols, polyester amide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyl alkanes, castor oil, or mixtures thereof may be used in combination.
• the ratio of the polyester polyol (A1) in the polyol composition (A) is preferably 1 to 50% by mass, and more preferably 1 to 40% by mass.
• the polyisocyanate composition (B) used in the present invention is a composition containing a polyisocyanate compound as a main component.
• known compounds can be used without any particular limitation, and they can be used alone or in combination.
• polyisocyanates having an aromatic structure in the molecular structure such as tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, NCO groups of these polyisocyanates A part of which is modified with carbodiimide;
• Alphanate compounds derived from these polyisocyanates include polyisocyanates having an alicyclic structure in the molecular structure such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3- (isocyanatomethyl) cyclohexane; Linear aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, and the alphanate compounds; isocyanurates of these polyisocyanates; allophanates derived from these polyisocyanates; Bilet bodies derived from these polyisocyanates; trimethylolpropane-modified adduct bodies;
• polyisocyanate which is a reaction product of various polyisocyanate compounds described above and a polyhydric alcohol.
• the polyhydric alcohol is a polyhydric alcohol which is a raw material of the polyol composition (A), the polyester polyol (A1), Polyester polyol (A1-2), polyester polyol not using polyethylene terephthalate as a raw material, polyether polyol, polyurethane polyol, polyether ester polyol, polyester (polyurethane) polyol, polyether (polyurethane) polyol, polyester amide polyol, acrylic polyol Polymer polyols selected from polycarbonate polyols, polyhydroxyl alkanes, castor oil or mixtures thereof can be used. .
• the polyisocyanate which is a reaction product of the above-mentioned various polyisocyanates and the said polyester polyol (A1).
• the reaction ratio between the polyisocyanate compound and the polyhydric alcohol is such that the equivalent ratio of isocyanate group to hydroxyl group [isocyanate group / hydroxyl group] is in the range of 1.0 to 5.0. It is preferable from the viewpoint of balance between strength and flexibility.
• the polyisocyanate compound preferably has an average molecular weight in the range of 100 to 1000 from the viewpoint of adhesive strength, heat resistance, and content resistance.
• the reactive adhesive used in the present invention is an adhesive that cures by a chemical reaction between an isocyanate group and a hydroxyl group, and can be used as a solvent-type or solvent-free type adhesive.
• the “solvent” of the solventless adhesive referred to in the present invention refers to a highly soluble organic solvent capable of dissolving the polyisocyanate compound and polyol compound used in the present invention.
• highly soluble organic solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, Toluol, xylol, n-hexane, cyclohexane and the like can be mentioned.
• MEK methyl ethyl ketone
• the adhesive of the present invention may be appropriately diluted with the organic solvent having high solubility according to the desired viscosity.
• either one of the polyisocyanate composition (B) or the polyol composition (A) may be diluted, or both may be diluted.
• organic solvents used in such cases include methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, xylol, n-hexane, cyclohexane, and the like. Is mentioned. Among these, ethyl acetate and methyl ethyl ketone (MEK) are preferable from the viewpoint of solubility, and ethyl acetate is particularly preferable.
• the amount of organic solvent used depends on the required viscosity, but is generally in the range of 20 to 50% by mass.
• the blending ratio of the polyisocyanate composition (B) and the polyol composition (A) is in the polyisocyanate compound contained in the polyisocyanate composition (B).
• the equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group and the hydroxyl group in the polyol compound contained in the polyol composition (A) is in the range of 0.6 to 5.0. From the viewpoint of excellent heat resistance at the time, the range of 1.0 to 3.5 is particularly preferable because these performances become remarkable.
• the reactive adhesive of the present invention comprises the polyol composition (A) and the polyisocyanate composition (B) as essential components, and further includes an aliphatic cyclic amide compound.
• Either the polyol composition (A) or the polyisocyanate composition (B) is mixed with one of the components, or is blended at the time of coating as a third component, whereby an aromatic amine is formed in the laminate package. Elution into the contents of the representative harmful low molecular chemical substances can be effectively suppressed.
• Examples of the aliphatic cyclic amide compound used here include ⁇ -valerolactam, ⁇ -caprolactam, ⁇ -enanthol lactam, ⁇ -capryllactam, ⁇ -propiolactam, and the like.
• ⁇ -caprolactam is preferable because it is excellent in reducing the amount of low-molecular chemical substances eluted.
• the blending amount is preferably such that the aliphatic cyclic amide compound is mixed in the range of 0.1 to 5 parts by mass per 100 parts by mass of the polyol component A.
• the catalyst used in the present invention is not particularly limited as long as it is for accelerating the urethanation reaction.
• metal catalysts amine catalysts, diazabicycloundecene (DBU), aliphatic cyclic amide compounds
• a catalyst such as a titanium chelate complex can be used.
• metal catalysts include metal complex systems, inorganic metal systems, and organic metal systems.
• metal complex systems include Fe (iron), Mn (manganese), Cu (copper), and Zr (zirconium). ), Th (thorium), Ti (titanium), Al (aluminum), Sn (tin), Zn (zinc), Bi (bismuth) and Co (cobalt) acetylacetonate salts of metals selected from the group
• iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zirconia acetylacetonate and the like can be mentioned.
• iron acetylacetonate Fe (acac) 3
• manganese acetylacetonate Mn (acac) 2
• Mn (acac) 2 manganese acetylacetonate
• the inorganic metal catalyst examples include a catalyst selected from Fe, Mn, Cu, Zr, Th, Ti, Al, Sn, Zn, Bi, Co, and the like.
• organometallic catalysts include stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, Examples thereof include nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, bismuth naphthenate, and bismuth neodecanoate. Of these, preferred compounds are organotin catalysts, and more preferred are stannous dioctate and dibutyltin dilaurate.
• the tertiary amine catalyst is not particularly limited as long as it is a compound having the above structure, and examples thereof include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, and 2-methylquinuclidine. Among these, triethylenediamine and 2-methyltriethylenediamine are preferable because of their excellent catalytic activity and industrial availability.
• tertiary amine catalysts include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ′′, N "-Pentamethyldiethylenetriamine, N, N, N ', N", N "-pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N', N", N "-pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N, N-dimethyl-N ′-(2-hydroxy Ethyl) ethylenediamine, N, N-dimethyl-N ′-(2-hydroxyethyl) propanediamine, bis Dimethyla
• Examples of the aliphatic cyclic amide compound include ⁇ -valerolactam, ⁇ -caprolactam, ⁇ -enanthol lactam, ⁇ -capryllactam, ⁇ -propiolactam, and the like. Among these, ⁇ -caprolactam is more effective for promoting curing.
• the titanium chelate complex is a compound whose catalytic activity is enhanced by ultraviolet irradiation, and is preferably a titanium chelate complex having an aliphatic or aromatic diketone as a ligand from the viewpoint of excellent curing acceleration effect.
• those having an alcohol having 2 to 10 carbon atoms in addition to an aromatic or aliphatic diketone as a ligand are preferred from the viewpoint that the effects of the present invention become more remarkable.
• the catalysts may be used alone or in combination.
• the mass ratio of the catalyst is preferably in the range of 0.001 to 80 parts, preferably in the range of 0.01 to 70 parts, when the mixed liquid of the polyisocyanate composition (B) and the polyol composition (A) is 100 parts. More preferred.
• the reactive adhesive of the present invention may be used in combination with a pigment, if necessary.
• usable pigments are not particularly limited.
• examples thereof include organic pigments and inorganic pigments such as pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearl pigments, and plastic pigments.
• specific examples of these colorants include various types, and examples of organic pigments include various insoluble azo pigments such as Bench Gin Yellow, Hansa Yellow, Raked 4R, etc .; Soluble properties such as Raked C, Carmine 6B, Bordeaux 10 and the like.
• Azo pigments include various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant dye pigments such as quinoline lake and fast sky blue; anthraquinone Various vat dyes such as pigments, thioindigo pigments and perinone pigments; various quinacridone pigments such as Cincacia Red B; various dioxazine pigments such as dioxazine violet; various condensed azos such as chromoftal Pigment; aniline black, etc. And the like.
• inorganic pigments include various chromates such as chrome lead, zinc chromate, and molybdate orange; various ferrocyan compounds such as bitumen; titanium oxide, zinc white, mapico yellow, iron oxide, bengara, chrome oxide Various metal oxides such as green and zirconium oxides; various sulfides or selenides such as cadmium yellow, cadmium red and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types such as calcium silicate and ultramarine blue Silicates; 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 oxides Click pigments, micaceous iron oxide pigments such as metallic pigment and pearl pigment; graphite, carbon black and the like.
• extender pigments examples include precipitated barium sulfate, powder, precipitated calcium carbonate, calcium bicarbonate, cryolite, alumina white, silica, hydrous finely divided silica (white carbon), ultrafine anhydrous silica (Aerosil), and silica sand (silica). Sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, ocher and the like.
• plastic pigment examples include “Grandall PP-1000” and “PP-2000S” manufactured by DIC Corporation.
• the pigment used in the present invention since it is excellent in durability, weather resistance and design, inorganic oxides such as titanium oxide and zinc white as a white pigment, and carbon black as a black pigment are more preferable.
• the mass ratio of the pigment used in the present invention is 1 to 400 parts by mass, particularly 10 to 300 parts by mass with respect to a total of 100 parts by mass of the isocyanate component B and the polyol component A. More preferable.
• adhesion promoter an adhesion promoter can also be used together with the reactive adhesive used in the present invention.
• adhesion promoter include silane coupling agents, titanate coupling agents, aluminum coupling agents, and epoxy resins.
• silane coupling agent examples include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, and N- ⁇ (aminoethyl) - ⁇ .
• Amino silanes such as aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane; ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycyl Epoxy silanes such as Sidoxypropyltriethoxysilane; Vinylsilanes such as Vinyltris ( ⁇ -methoxyethoxy) silane, Vinyltriethoxysilane, Vinyltrimethoxysilane, ⁇ -Methacryloxypropyltrimethoxysilane; Hexamethyldisilazane, ⁇ -Me Mercaptopropyl trimethoxysilane and the like.
• titanate coupling agents examples include tetraisopropoxy titanium, tetra-n-butoxy titanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium etc. can be mentioned.
• examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.
• epoxy resins there are 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, many Various epoxy resins such as carboxylic acid ester type, aminoglycidyl type, resorcin type, triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, acrylic glycidyl Ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycid
• the reactive adhesive used in the present invention may contain other additives other than those described above.
• additives include leveling agents, inorganic fine particles such as colloidal silica and alumina sol, polymethyl methacrylate organic fine particles, antifoaming agents, anti-sagging agents, wetting and dispersing agents, viscosity modifiers, ultraviolet absorbers, metals Deactivator, peroxide decomposer, flame retardant, reinforcing agent, plasticizer, lubricant, rust preventive, fluorescent brightener, inorganic heat absorber, flame retardant, antistatic agent, dehydrating agent, Known and commonly used thermoplastic elastomers, tackifiers, phosphoric acid compounds, melamine resins, or reactive elastomers can be used. The content of these additives can be appropriately adjusted and used within a range that does not impair the function of the reactive adhesive used in the present invention.
• adhesion promoters and additives may be mixed with one component of the polyisocyanate composition (B) or the polyol composition (A), or may be used as a third component by blending at the time of application. it can.
• blended components other than polyisocyanate composition (B) with the polyol composition (A) beforehand is prepared, and this premix and polyisocyanate composition (B) are just before construction. Prepare by mixing.
• the laminated film of the present invention is formed by laminating an adhesive layer made of the reactive adhesive between a first plastic film and a second plastic film. Specifically, the reactive adhesive is applied to a first plastic film, then a second plastic film is laminated on the coated surface, and the adhesive layer is cured.
• the reactive adhesive is a solventless type
• the reactive adhesive contains a solvent
• the first plastic film is applied by a roll coater coating method, passed through a drying oven at 60 ° C., and then another substrate is bonded.
• the coating conditions are preferably about 300 to 3000 mPa ⁇ s at 40 ° C. with a normal roll coater heated to 30 ° C. to 90 ° C., but the adhesive of the present invention is blended. Since the viscosity after leaving for 30 minutes in a 40 ° C. atmosphere is 5000 mPa ⁇ s or less, coating can be performed without any problem.
• the coating amount is preferably 0.5 to 5 g / m 2 , more preferably about 0.5 to 3 g / m 2 .
• a gravure or flexographic print of printing ink may be used on the first plastic film, and even in this case, a good laminate appearance can be exhibited.
• a solvent type, aqueous type or active energy ray curable ink can be used as the above-mentioned printing ink.
• the adhesive is cured in 12 to 72 hours at room temperature or under heating after laminating, and expresses practical physical properties.
• the first plastic film used here is a PET (polyethylene terephthalate) film, a nylon film, an OPP (biaxially oriented polypropylene) film, a K-coated film such as polyvinylidene chloride, a base film such as various deposited films, and an aluminum foil.
• the second plastic film include CPP (unstretched polypropylene) film, VMCP (aluminum vapor-deposited unstretched polypropylene film), LLDPE (linear low density polyethylene), and LDPE.
• sealant films such as (low density polyethylene), HDPE (high density polyethylene), and VMLDPE (aluminum vapor-deposited low density polyethylene film) films.
• an excellent laminated film appearance can be obtained not only when a high-speed laminating process is performed with a dry laminating machine having a drying step of an organic solvent in an adhesive, but also when a high-speed laminating process is performed with a solventless laminating machine.
• a high-speed laminating process is performed with a dry laminating machine having a drying step of an organic solvent in an adhesive
• a solventless laminating machine for example, in the case of a film configuration of PET (polyethylene terephthalate) film / VMPP (aluminum-deposited unstretched polypropylene film), 200 m / min or more, and in the case of an OPP / CPP film configuration, high-speed processing of 350 m / min or more is satisfactory. Appearance can be exhibited.
• the package of the present invention is formed by forming the laminated film into a bag shape. Specifically, the package is formed by heat-sealing the laminated film.
• required performance easy tearability and hand cutability
• rigidity and durability required for the package for example, impact resistance, pinhole resistance, etc.
• Other layers can be laminated as required. Usually, it is used with a base material layer, a paper layer, a second sealant layer, a non-work cloth layer and the like.
• a method of laminating other layers a known method can be used.
• an adhesive layer may be provided between other layers and laminated by a dry laminate method, a heat laminate method, a heat seal method, an extrusion laminate method, or the like.
• the adhesive the reactive adhesive may be used, or other one-component type urethane adhesive, epoxy adhesive, aqueous dispersion of acid-modified polyolefin, or the like may be used.
• the first plastic film layer / adhesive layer / second plastic layer, first plastic layer which can be suitably used for general packaging bodies, lid materials, refill containers, etc.
• a second plastic layer / paper that can be suitably used for a base layer / adhesive layer / first plastic film layer / adhesive layer / second plastic layer, paper container, paper cup, etc.
• These laminates may have a print layer, a top coat layer, or the like as necessary.
• the first plastic film layer includes, for example, a polyester resin film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polylactic acid (PLA); a polyolefin resin film such as polypropylene; a polystyrene resin film; a nylon 6, a poly- Polyamide resin film such as p-xylylene adipamide (MXD6 nylon); Polycarbonate resin film; Polyacrylonitrile resin film; Polyimide resin film; Multilayers thereof (for example, nylon 6 / MXD6 / nylon 6, nylon 6 / An ethylene-vinyl alcohol copolymer / nylon 6) or a mixture is used. Among them, those having mechanical strength and dimensional stability are preferable. Of these, a film arbitrarily stretched in the biaxial direction is preferably used.
• a polyester resin film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polylactic acid (PLA); a polyolefin
• the first plastic film layer is made of a soft metal foil such as an aluminum foil to provide a barrier function, as well as a vapor deposition layer such as aluminum vapor deposition, silica vapor deposition, alumina vapor deposition, and silica alumina binary vapor deposition; vinylidene chloride resin
• a soft metal foil such as an aluminum foil to provide a barrier function
• a vapor deposition layer such as aluminum vapor deposition, silica vapor deposition, alumina vapor deposition, and silica alumina binary vapor deposition
• vinylidene chloride resin An organic barrier layer made of modified polyvinyl alcohol, ethylene vinyl alcohol copolymer, MXD nylon or the like can be used.
• a conventionally known sealant resin can be used as the second plastic film layer.
• polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE), acid-modified polyethylene, polypropylene (PP), acid-modified polypropylene, copolymerized polypropylene, ethylene-vinyl acetate
• polyolefin resins such as copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene- (meth) acrylic acid copolymers, and ionomers.
• polyethylene resins are preferred from the viewpoint of low temperature sealing properties, and polyethylene is particularly preferred because of its low cost.
• the thickness of the sealant layer is not particularly limited, but is preferably in the range of 10 to 60 ⁇ m and more preferably in the range of 15 to 40 ⁇ m in consideration of processability to packaging materials and heat sealability. Further, by providing the sealant layer with irregularities with a height difference of 5 to 20 ⁇ m, it is possible to impart slipperiness and tearability of the packaging material to the sealant layer. *
• paper layers include natural paper and synthetic paper.
• the first and second sealant layers can be formed of the same material as the above-described sealant layer. You may provide a printing layer in the outer surface or inner surface side of a base material layer and a paper layer as needed. *
• the “other layer” may contain a known additive or stabilizer, for example, an antistatic agent, an easy adhesion coating agent, a plasticizer, a lubricant, an antioxidant, or the like.
• a known additive or stabilizer for example, an antistatic agent, an easy adhesion coating agent, a plasticizer, a lubricant, an antioxidant, or the like.
• other layers are those in which the surface of the film has been subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. as a pretreatment in order to improve adhesion when laminated with other materials. May be. *
• a gobeltop-type bottomed container a tetra classic container
• a backpack type a tube container
• a paper cup a lid material, etc.
• an easy-opening treatment or resealability means may be provided as appropriate in the package of the present invention.
• the laminate obtained in this way can be used in various applications, such as packaging materials for foods and pharmaceuticals, daily necessities, barrier materials, roofing materials, solar cell panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting.
• the rectifying column was removed and switched to a glass condenser, and a line was connected from a nitrogen gas inlet tube to a vacuum pump, and a condensation reaction was performed for 5 hours under a reduced pressure of 50 Torr.
• the temperature was lowered to 130 ° C., and ethyl acetate was added and diluted using a dropping funnel to obtain a PET-containing polyester polyol (A1-1).
• Tables 1 and 2 show the weight fraction of the PET pellets when the raw materials are charged, the solid-converted acid value, the solid-converted hydroxyl value, the solid content, and the number-average molecular weight of the obtained PET-decomposed polyester polyol (A1-11).
• a polyester polyol (A1-12) was obtained.
• Tables 1 and 2 show the weight fraction of the PET pellets when the raw materials are charged and the solid acid value, solid hydroxyl value, solid content, and number average molecular weight of the obtained PET-decomposed polyester polyol (A1-12).
• Examples and Comparative Examples The reactive adhesives for Examples and Comparative Examples were prepared by blending the polyol composition (A) and the polyisocyanate composition (B) shown in Tables 5 to 7.
• the isocyanate (B) is a trifunctional polyisocyanate obtained by adding tolylene diisocyanate (TDI) to commercially available trimethylolpropane (TMP) (product name: DIC Dick Dry KW-75, TDI TMP addition product, solid content 75 %) was used.
• TMP trimethylolpropane
• a laminated film was prepared and evaluated according to the method of each evaluation item, and evaluated according to the evaluation criteria. The results are shown in Tables 5-7.
• a dry laminator (Musashino Machine Design Office, dry lami test coater) is used as the laminating machine, the processing speed is 250 m / min, and the first plastic film layer is a PET film (commercial polyethylene terephthalate film).
• the adhesives of Examples or Comparative Examples so that the application amount was 3 g / m 2
• VMCP commercially available aluminum-deposited unstretched polypropylene film
• the appearance of the film immediately after laminating (whether there are defects such as wrinkles, bubbles due to bubbles, tunneling caused by misalignment between films) was judged based on the following evaluation criteria using visual and scale loupes.
• the evaluation with a scale loupe was performed with the number of bubbles in a 1 cm 2 scale.
• ⁇ Wrinkles and tunneling occur in many places with 17 or more bubbles.
• a dry laminator (Musashino Machine Design Office, dry lami test coater) was used as the laminating machine, the processing speed was 250 m / min, and PET-AL (commercially available aluminum foil was bonded as the first plastic film layer) Polyethylene terephthalate) was coated with the adhesive of Example or Comparative Example so that the coating amount was 4.3 g / m 2, and then CPP (commercial unstretched polypropylene film) was laminated as the second plastic film layer. Thereafter, aging was performed at 40 ° C. for 5 days to obtain a laminated film.
• the evaluation method uses a Tensilon universal testing machine manufactured by Orientec Co., Ltd., cuts out a 15 mm wide test piece from the pouch after retort treatment, wipes the contents well, and then has an atmosphere temperature of 25 ° C. and a peeling speed of 300 mm / min.
• the tensile strength when peeled by the 180 degree peeling method was compared as the adhesive strength.
• the unit of adhesive strength was N / 15 mm. If the adhesive strength is 5 N / 15 mm or more, it can be said that it is practically sufficient.
• a dry laminator (Musashino Machine Design Office, dry lami test coater) was used as the laminating machine, the processing speed was 250 m / min, and the first plastic film layer was Nyl (commercial nylon film). Or after apply
• coating the adhesive agent of a comparative example so that the application quantity might be 4.3 g / m ⁇ 2 >, LLDPE (commercially available linear low density polyethylene film) was laminated as a 2nd plastic film layer. Thereafter, aging was performed at 40 ° C. for 5 days to obtain a laminated film. A pouch having a size of 120 mm ⁇ 120 mm was prepared using the obtained laminated film, and 70 g of Super sol pH 13 was filled in the pouch as a content. Thereafter, treatment was performed for 3 days in a thermostatic bath at 50 ° C., and evaluation was performed by measuring peel strength.
• the evaluation method is a Tensilon universal testing machine manufactured by Orientec Co., Ltd., a test piece having a width of 15 mm is cut out from the pouch after the content resistance test, the content is thoroughly wiped, and the atmosphere temperature is 25 ° C., and the peeling speed is 300 mm. / Min, the tensile strength when peeled by the 180 degree peeling method was compared as the adhesive strength.
• the unit of adhesive strength was N / 15 mm. If the adhesive strength is 2 N / 15 mm or more, it can be said that it is practically sufficient.
• Adhesive strength 7 N / 15 mm or more B: Adhesive strength 5 N / 15 mm or more, less than 7 N / 15 mm
• ⁇ Adhesive strength 1 N / 15 mm or more, less than 2 N / 15 mm
• X Adhesive strength less than 1 N / 15 mm
• the reactive adhesive of the present invention can be applied as an adhesive for a laminate in which various plastic films, metal vapor-deposited films or metal foils are appropriately combined, and is high even under high-speed coating conditions. Not only can a laminated film having excellent adhesion and appearance after lamination be obtained, but also a laminated film having excellent heat resistance and content resistance can be obtained.

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• Medicinal Chemistry (AREA)
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• 2019
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