CN117460802A - Adhesive, laminate, and packaging material - Google Patents

Adhesive, laminate, and packaging material Download PDF

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Publication number
CN117460802A
CN117460802A CN202280041016.XA CN202280041016A CN117460802A CN 117460802 A CN117460802 A CN 117460802A CN 202280041016 A CN202280041016 A CN 202280041016A CN 117460802 A CN117460802 A CN 117460802A
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China
Prior art keywords
acid
polyol
adhesive
composition
examples
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CN202280041016.XA
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Chinese (zh)
Inventor
细野月子
广田安信
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DIC Corp
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DIC Corp
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • 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
    • 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
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides a 2-liquid curing adhesive with excellent boiling resistance and resolubility resistance of a printing layer, a laminated body obtained by using the adhesive and a packaging material. A2-liquid curable adhesive comprising a polyol composition (X) and a polyisocyanate composition (Y), wherein the polyol composition (X) comprises a polyester polyol (A) which is the reaction product of a polyvalent alcohol (a) and a polycarboxylic acid (b), the polyisocyanate composition (Y) comprises a urethane prepolymer (C) which is the reaction product of a polyol composition (Y) comprising a polyester polyol (C ' 1) and an isocyanate compound (C ' 2), and the polyester polyol (C ' 1) is the reaction product of a polyvalent alcohol (C) and a polycarboxylic acid (d), and the polyvalent alcohols (a) and (C) each comprise diols (a 1) and (C1) having only 1 alkyl side chain, and the total amount of the diols (a 1) and (C1) is 5% by mass or more and 20% by mass or less of the total amount of the polyol composition (X) and the polyisocyanate composition (Y).

Description

Adhesive, laminate, and packaging material
Technical Field
The present invention relates to an adhesive, a laminate obtained by using the adhesive, and a packaging material.
Background
Laminates used for various packaging materials, labels, and the like are provided with design properties, functionality, storage properties, convenience, conveyance resistance, and the like by lamination of various and various plastic films, metal foils, paper, and other substrates. Packaging materials obtained by forming the laminate into a bag are used as packaging materials for foods, medicines, lotions and the like.
Conventionally, a laminate used for a packaging material is mainly a laminate obtained by a dry lamination method in which an adhesive (sometimes referred to as a solvent-based laminating adhesive) dissolved in a volatile organic solvent is applied to a base material, and the organic solvent is volatilized during passage through an oven to bond other base materials, but in recent years, from the viewpoints of reducing environmental load and improving working environment, there has been an increasing demand for a reactive 2-liquid-type laminating adhesive (hereinafter referred to as a solvent-free adhesive) containing no volatile organic solvent (patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2014-159548
Disclosure of Invention
Problems to be solved by the invention
The solvent-free adhesive has many advantages such as no drying step, no solvent discharge, energy saving, low running cost, and no concern of solvent residue in a laminate obtained by bonding plastic films to each other or a laminate obtained by bonding a plastic film to a metal foil or a metal deposition layer. On the other hand, the components used in the solvent-free adhesive are required to have low molecular weights so as to have a viscosity that can be applied when heated to about 40 to 100 ℃, and there is a problem that the boiling resistance of the laminate is not at a satisfactory level.
In the laminate for packaging materials, a printed layer is generally provided on the back side of a base material that is the outermost layer (as viewed from the content) with a printing ink, and the printed layer is bonded to other base materials via an adhesive. The low molecular weight polyol used in the solvent-free adhesive also has a problem of easy redissolution of the printed layer.
The present invention has been made in view of such circumstances, and an object thereof is to provide a 2-liquid curable adhesive which is excellent in boiling resistance and resolubility resistance of a printed layer even when the molecular weight is low, and a laminate and a packaging material obtained using the adhesive.
Means for solving the problems
The present invention relates to a 2-liquid curable adhesive comprising a polyol composition (X) and a polyisocyanate composition (Y), wherein the polyol composition (X) comprises a polyester polyol (a) which is a reaction product of a composition comprising a polyvalent alcohol (a) and a polycarboxylic acid (b), the polyisocyanate composition (Y) comprises a urethane prepolymer (C) which is a reaction product of a polyol composition (Y) comprising a polyester polyol (C ' 1) and an isocyanate compound (C ' 2), the polyester polyol (C ' 1) is a reaction product of a polyvalent alcohol (C) and a polycarboxylic acid (d), the polyvalent alcohol (a) comprises a diol (a 1) having only 1 alkyl side chain, the polyvalent alcohol (C) comprises a diol (C1) having only 1 alkyl side chain, and the total amount of the diol (a 1) and the diol (C1) is 5% by mass or more and 20% by mass or less of the total amount of the polyol composition (X) and the polyisocyanate composition (Y).
Effects of the invention
The adhesive of the present invention can provide a laminate or packaging material having excellent boiling resistance and good appearance.
Detailed Description
< adhesive >
The adhesive of the present invention is a 2-liquid curable adhesive comprising a polyol composition (X) and a polyisocyanate composition (Y). The adhesive of the present invention will be described in detail below.
(polyol composition (X))
(polyester polyol (A))
The polyol composition (X) used in the adhesive of the present invention contains a polyester polyol (a) which is a reaction product of a composition containing a polyvalent alcohol (a) and a polyvalent carboxylic acid (b). In addition, the polyvalent alcohol (a) contains a diol (a 1) having only 1 alkyl side chain. This makes it possible to produce an adhesive having excellent boiling resistance.
Examples of the diol (a 1) include 1, 2-propanediol, 2-methyl-1, 3-propanediol, and 3-methyl-1, 5-pentanediol.
The polyhydric alcohol (a) that can be used in combination with the diol (a 1) may be a conventionally known polyhydric alcohol, and is not particularly limited. Examples of the 2-functional alcohol include aliphatic diols such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, dimethylbutanediol, butylethylpropanediol, 2, 4-trimethyl-1, 3-pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dihydroxyethoxybenzene, 1, 4-cyclohexanediol, and 1, 4-cyclohexanedimethanol;
Ether diols such as polyoxyethylene glycol and polyoxypropylene glycol;
modified polyether diols obtained by ring-opening polymerization of aliphatic diols with 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, allyl glycidyl ether, and the like;
lactone-based polyester polyols obtained by polycondensation of aliphatic diols with various lactones such as lactone (Japanese text), epsilon-caprolactone, etc.;
bisphenol such as bisphenol A and bisphenol F;
alkylene oxide adducts of bisphenols such as ethylene oxide and propylene oxide obtained by adding bisphenol such as bisphenol A and bisphenol F.
Examples of the polyol having 3 or more functions include aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerol, hexanetriol and pentaerythritol;
modified polyether polyols obtained by ring-opening polymerization of aliphatic polyols with 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, allyl glycidyl ether and the like;
And lactone-based polyester polyols obtained by polycondensation of aliphatic polyols with various lactones such as epsilon-caprolactone.
The polyvalent alcohol (a) preferably contains diethylene glycol, from the viewpoint of excellent effect of suppressing resolubilization for printing when the adhesive is applied to the printing layer. The proportion of diethylene glycol to the polyvalent alcohol (a) other than the diol (a 1) is preferably 50% by mass or more, more preferably 60% by mass or more.
Examples of the polycarboxylic acid (b) include aromatic polycarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1, 4-naphthalenedicarboxylic acid, 2, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic anhydride, naphthalenedicarboxylic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyl dicarboxylic acid, 1, 2-bis (phenoxy) ethane-p, p' -dicarboxylic acid, benzophenone tetracarboxylic acid dianhydride, isophthalic acid-5-sodium sulfonate, tetrachlorophthalic anhydride, tetrabromophthalic anhydride and the like;
methyl esters of aromatic polybasic acids such as dimethyl terephthalate and dimethyl 2, 6-naphthalate;
aliphatic polybasic acids such as malonic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic anhydride, and itaconic acid;
Alkyl esters of aliphatic polybasic acids such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate;
1, 1-cyclopentanedicarboxylic acid, 1, 2-cyclopentanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1, 2, 4-tricarboxylic acid-1, 2-anhydride, humic anhydride (water-soluble material of 3-terminal acid, japanese text) and alicyclic polybasic acids such as chlorobridge anhydride may be used in combination of 1 or 2 or more kinds.
The polycarboxylic acid (b) preferably comprises adipic acid. Thus, the effect of reducing the viscosity of the polyester polyol (a) and improving the pot life and coating suitability at low temperatures can be expected. In addition, it is expected that the wettability of the adhesive to the substrate improves and the appearance of the laminate becomes more excellent. The blending amount of adipic acid may be appropriately adjusted depending on the coating conditions and the like, and is preferably 40% by mass or more, more preferably 60% by mass or more of the polycarboxylic acid (b), as an example. The entire amount of the polycarboxylic acid (b) may be adipic acid.
When an aromatic polycarboxylic acid is used as the polycarboxylic acid (b), boiling resistance is improved, while wettability to a substrate tends to be lowered and pot life tends to be shortened. The adhesive of the present invention has sufficient boiling resistance even when the amount of the aromatic polycarboxylic acid used is small or not used at all, and therefore, the amount of the aromatic polycarboxylic acid blended in the polycarboxylic acid (b) is preferably 15 mass% or less, more preferably 10 mass% or less.
The number average molecular weight of the polyester polyol (a) is not particularly limited, but is preferably 350 to 5,000. The number average molecular weight in the present specification is calculated from the actual measurement value of the designed functional group number and hydroxyl value (mgKOH/g) according to the following formula. The hydroxyl value can be measured by the hydroxyl value measuring method described in JIS-K0070.
[ mathematics 1]
The number of functional groups is calculated from the number of moles (O) of carboxyl groups, the number of moles (P) of polycarboxylic acids, the number of moles (Q) of hydroxyl groups, and the number of moles (R) of polyvalent alcohols contained in the composition as a raw material of the polyester polyol (A) by (Q+O)/(R+P).
The blending amount of the polyester polyol (a) is preferably 60 mass% or more of the solid content of the polyol composition (X). This enables to produce an adhesive having excellent boiling resistance and resolubility resistance of the printed layer.
(polyol (B))
The polyol composition (X) may contain a polyol (B) other than the polyester polyol (a). Examples of the polyol (B) include, but are not limited to, 2-functional and 3-functional or more alcohols similar to those exemplified as the polyvalent alcohol (a), polyurethane polyols, polyester polyols, polyether polyols, polyester polyurethane polyols, polyether polyurethane polyols, castor oil, dehydrated castor oil, hydrogenated castor oil which is a hydride of castor oil, castor oil-based polyols such as 5 to 50 mol adducts of alkylene oxide of castor oil, and mixtures thereof.
The blending amount of the polyol (B) is not particularly limited, but is preferably 40 mass% or less based on the total amount of the polyester polyol (a).
When the adhesive of the present invention is used in the form of a solvent-free type, the viscosity of the polyol composition (X) is adjusted to a range suitable for the solvent-free lamination method. As an example, the viscosity at 40 ℃ is adjusted so as to be in the range of 100 to 5000mPas, more preferably 100 to 3000 mPas. As an example, the viscosity of the polyol composition (X) can be adjusted by the skeleton of the polyester polyol (a) and a plasticizer described later.
(polyisocyanate composition (Y))
The isocyanate composition (Y) contains a urethane prepolymer (C) obtained by reacting a polyol composition (Y) containing a polyester polyol (C '1) with an isocyanate compound (C' 2) having a plurality of isocyanate groups in an excess of isocyanate groups. In addition, the polyester polyol (C' 1) is a reaction product of a composition comprising a polyvalent alcohol (C) comprising a diol (C1) having only 1 alkyl side chain and a polycarboxylic acid (d). This makes it possible to produce an adhesive having excellent boiling resistance. As the diol (c 1), the same diol as the diol (a 1) can be used.
The polyvalent alcohol (c) may contain a polyvalent alcohol other than the diol (c 1). As the polyvalent alcohol that can be used in combination with the diol (c 1), the same polyvalent alcohol as exemplified for the polyvalent alcohol (a) can be used.
As the polycarboxylic acid (d), the same polycarboxylic acids as exemplified for the polycarboxylic acid (b) can be used. The polycarboxylic acid (d) preferably comprises adipic acid. Thus, the effect of reducing the viscosity of the polyester polyol (C' 1) and further the urethane prepolymer (C) and improving the pot life and the coating suitability at low temperature can be expected. In addition, it is expected that the wettability of the adhesive to the substrate improves and the appearance of the laminate becomes more excellent. The blending amount of adipic acid may be appropriately adjusted depending on the coating conditions and the like, and is preferably 40% by mass or more, more preferably 60% by mass or more of the polycarboxylic acid (d), as an example. The entire amount of the polycarboxylic acid (d) may be adipic acid.
When an aromatic polycarboxylic acid is used as the polycarboxylic acid (d), boiling resistance is improved, while wettability to a substrate tends to be lowered and pot life tends to be shortened. The adhesive of the present invention has sufficient boiling resistance even when the amount of the aromatic polycarboxylic acid used is small or not used at all, and therefore, the amount of the aromatic polycarboxylic acid blended in the polycarboxylic acid (d) is preferably 15 mass% or less, more preferably 10 mass% or less.
The number average molecular weight of the polyester polyol (C' 1) is not particularly limited, and is, for example, 400 to 10,000, more preferably 500 to 2,000.
The isocyanate compound (C' 2) is not particularly limited, and examples thereof include aromatic diisocyanates, aromatic aliphatic diisocyanates, alicyclic diisocyanates, biuret, allophanate, adduct, allophanate, carbodiimide-modified, uretdione-modified, and the like of these diisocyanates, and these may be used singly or in combination of plural kinds.
Examples of the aromatic diisocyanate include 2,2' -diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate (also referred to as polymeric MDI or crude MDI), 1, 3-phenylene diisocyanate, 4' -diphenyl diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -toluidine diisocyanate, 2,4, 6-triisocyanate toluene, 1,3, 5-triisocyanate benzene, dianisidine diisocyanate, 4' -diphenyl ether diisocyanate, 4',4 "-triphenylmethane triisocyanate, and the like, but are not limited thereto.
The aromatic aliphatic diisocyanate is an aliphatic isocyanate having 1 or more aromatic rings in the molecule, and examples thereof include, but are not limited to, m-xylylene diisocyanate (alias: XDI), α, α, α ', α' -tetramethylxylylene diisocyanate (alias: TMXDI), and the like.
Examples of the aliphatic diisocyanate include, but are not limited to, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also referred to as HDI), pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, and 2, 4-trimethylhexamethylene diisocyanate.
Examples of the alicyclic diisocyanate include 3-isocyanatomethyl-3, 5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (alias: IPDI), 1, 3-cyclopentanediisocyanate, 1, 3-cyclohexanediisocyanate, 1, 4-cyclohexanediisocyanate, methyl-2, 6-cyclohexanediisocyanate, 4' -methylenebis (cyclohexylisocyanate), 1, 4-bis (isocyanatomethyl) cyclohexane, and the like, but are not limited thereto.
From the viewpoints of initial cohesion and shortening of curing time, it is preferable to use an aromatic diisocyanate and/or a derivative thereof.
In addition, the polyol composition (y) may contain a polyether polyol (C' 3). This improves the wettability of the adhesive to the substrate, and can provide a laminate having a more excellent appearance. In addition, the polyisocyanate composition (Y) may cause turbidity during long-term storage, but this can be suppressed.
The polyether polyol (C' 3) is not particularly limited, and examples thereof include those obtained by polymerizing an alkylene oxide (japanese text: zerun) compound such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc., with a low molecular weight polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, etc., as an initiator, and 1 or 2 or more kinds of the polyether polyols may be used in combination. The number of functional groups of the polyether polyol (b 2) is not particularly limited, and a polyether polyol having 3 or more functions may be used in addition to 2 functions. Preferably, a 2-functional or 3-functional polypropylene glycol is used.
The number average molecular weight of the polyether polyol (C' 3) is not particularly limited, and is, for example, 200 to 10,000, more preferably 400 to 2,000.
In the case of using the polyether polyol (C ' 3) in combination, the blending amount thereof is preferably 5% by mass or more and 50% by mass or less of the total amount of the polyester polyol (C ' 1) and the polyether polyol (C ' 3). From the viewpoint of balance with boiling resistance, it is more preferably 5 mass% or more and 35 mass% or less.
The urethane prepolymer (C) is obtained by reacting the polyol composition (y) and the isocyanate compound (C' 2) under the condition of excessive isocyanate groups. The ratio [ NCO ]/[ OH ] of the number of moles [ NCO ] of isocyanate groups to the number of moles [ OH ] of hydroxyl groups to be supplied to the reaction is preferably 1.0 to 3.0. More preferably 1.5 to 2.0.
The polyisocyanate composition (Y) may contain a polyisocyanate compound (D) other than the urethane prepolymer (C). Examples of the polyisocyanate compound (D) include a compound exemplified as the isocyanate compound (C' 2), a urethane prepolymer as a reaction product of these isocyanate compounds and a polyol, and the like, and 1 or 2 or more kinds of the compounds may be used in combination.
When the adhesive of the present invention is used in the form of a solvent-free type, the viscosity of the polyisocyanate composition (Y) is adjusted to a range suitable for the solvent-free lamination method. As an example, the viscosity at 40 ℃ is adjusted so as to be in the range of 500 to 5000mPas, more preferably 500 to 3000 mPas. As an example, the viscosity of the polyisocyanate composition (Y) can be adjusted by the amount of the low molecular weight isocyanate compound contained in the polyisocyanate composition (Y).
In the adhesive of the present invention, the ratio of the total amount of the diols (a 1) and (c 1) used in the preparation of the adhesive to the solid content of the adhesive is 5% by mass or more and 20% by mass or less. This makes it possible to produce an adhesive which has excellent boiling resistance and does not easily redissolve the printed layer.
(other component of adhesive)
The adhesive of the present invention may contain components other than the above components. The other components may be contained in either or both of the polyol composition (X) and the polyisocyanate composition (Y), or may be prepared separately from them in advance and mixed with the polyol composition (X) and the polyisocyanate composition (Y) immediately before the adhesive is applied. The components will be described below.
(catalyst)
Examples of the catalyst include metal catalysts, amine catalysts, and aliphatic cyclic amide compounds.
Examples of the metal catalyst include metal complex catalysts, inorganic metal catalysts, and organic metal catalysts. Examples of the metal complex catalyst include acetylacetonates of metals selected from Fe (iron), mn (manganese), cu (copper), zr (zirconium), th (thorium), ti (titanium), al (aluminum), and Co (cobalt), for example, iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, and zirconium acetylacetonate oxide.
Examples of the inorganic metal catalyst include those selected from Sn, fe, mn, cu, zr, th, ti, al, co and the like.
Examples of the organometallic catalyst include organozinc compounds such as zinc octoate, zinc neodecanoate, zinc naphthenate, stannous diacetate, stannous dioctanoate, stannous dioleate, stannous dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, organotin compounds such as dibutyltin dichloride, organonickel compounds such as nickel octoate and nickel naphthenate, organocobalt compounds such as cobalt octoate and cobalt naphthenate, organobismuth compounds such as bismuth octoate, bismuth neodecanoate and bismuth naphthenate, organobismuth compounds such as tetraisopropyl oxytitanate (Japanese text), titanium dichloride, tetrabutyl titanate, titanium trichloride, titanium chelate compounds containing at least 1 of aliphatic diketones, aromatic diketones and alcohols having 2 to 10 carbon atoms as a ligand, and the like.
Examples of the amine-based catalyst include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N, N, N ', N' -tetramethylethylenediamine, N, N, N ', N' -tetramethylpropylenediamine, N, N, N ', N' -pentamethyldiethylenetriamine, N, N, N ', N' -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ', N' -pentamethyldipropylenetriamine, N, N, N ', N' -tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N, N-dimethyl-N '- (2-hydroxyethyl) ethylenediamine, N, N-dimethyl-N' - (2-hydroxyethyl) propylenediamine, bis (dimethylaminopropyl) amine, bis (dimethylaminopropyl) isopropanolamine, 3-quininol, N, N, N ', N' -tetramethylguanidine, 1,3, 5-tris (N, N-dimethylaminopropyl) hexahydro-s-triazine, 1, 8-diazabicyclo [5.4.0] undecene-7, N-methyl-N '- (2-dimethylaminoethyl) piperazine, N, N' -dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1, 2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropyl imidazole, N-dimethylhexylamine, N-methyl-N' - (2-hydroxyethyl) piperazine, 1- (2-hydroxyethyl) imidazole, 1- (2-hydroxypropyl) imidazole, 1- (2-hydroxyethyl) -2-methylimidazole, 1- (2-hydroxypropyl) -2-methylimidazole, and the like.
Examples of the aliphatic cyclic amide compound include delta-valerolactam, epsilon-caprolactam, omega-enantholactam, eta-caprylolactam and beta-propiolactam. Of these, epsilon caprolactam more effectively promotes curing.
(anhydride)
Examples of the acid anhydride include a cyclic aliphatic acid anhydride, an aromatic acid anhydride, and an unsaturated carboxylic acid anhydride, and 1 or 2 or more kinds of acid anhydrides may be used in combination. More specifically, examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, polysebacic anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhumic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, methylcyclohexenetetracarboxylic anhydride, ethylene glycol ditrimellitic acid dianhydride, chlorobridge anhydride, nadic anhydride, methylnadic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1, 2-dicarboxylic-1, 2,3, 4-tetrahydro-1-naphthalenesuccinic anhydride, 1-methyl-dicarboxyl-1, 2,3, 4-tetrahydro-1-naphthalenesuccinic anhydride, and the like.
Further, as the acid anhydride, a modified compound of the above compound with a glycol may be used. Examples of the diols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol, and neopentyl glycol; polyether glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol. Further, it is also possible to use copolymerized polyether glycol of 2 or more kinds of diols and/or polyether glycol among them.
(coupling agent)
Examples of the coupling agent include silane coupling agents, titanate coupling agents, and aluminum coupling agents.
Examples of the silane coupling agent include aminosilanes such as γ -aminopropyl triethoxysilane, γ -aminopropyl trimethoxysilane, N- β (aminoethyl) - γ -aminopropyl trimethyldimethoxysilane, and N-phenyl- γ -aminopropyl trimethoxysilane; epoxysilanes such as beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-epoxypropoxypropyltrimethoxysilane, gamma-epoxypropoxypropyltriethoxysilane and the like; vinyl silanes such as vinyl tris (β -methoxyethoxy) silane, vinyl triethoxysilane, vinyl trimethoxysilane, and γ -methacryloxypropyl trimethoxysilane; hexamethyldisilazane, gamma-mercaptopropyl trimethoxysilane, and the like.
Examples of the titanate-based coupling agent include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylglycol titanate, titanium lactate, and tetrastearyloxy titanium.
Examples of the aluminum-based coupling agent include aluminum acetoacetoxy diisopropoxide.
(pigment)
Examples of the pigment include, but are not particularly limited to, extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, organic pigments such as pearl pigments, inorganic pigments, and plastic pigments described in 1970 edition (edited by the japan paint industry).
Examples of extender pigments include precipitated barium sulfate, fine powder, precipitated calcium carbonate, calcium bicarbonate, gypsum rubrum, alumina white, silica, hydrous fine silica (white carbon), ultrafine anhydrous silica (AEROSIL), silica sand (silica sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, and loess.
Specific examples of the organic pigment include various insoluble azo pigments such as benzidine yellow, hansa yellow, lake red 4R, and the like; soluble azo pigments such as lake red C, carmine 6B, and date red 10; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various alkaline dyeing lakes such as rhodamine lake and methyl violet lake; quinoline lake, fast sky blue, and the like; various vat dye-based pigments such as anthraquinone-based pigments, thioindigo-based pigments, and viol-based pigments; various quinacridone pigments such as Cinquasia Red B; various dioxazine pigments such as dioxazine violet; various condensed azo pigments such as solid and transparent; nigrosine, etc.
Examples of the inorganic pigment include various chromates such as chrome yellow, zinc chromate, and molybdenum orange; various ferricyanide compounds such as Prussian blue; various metal oxides such as titanium oxide, zinc white, brown yellow, iron oxide, red iron oxide, chromium oxide green, and zirconium oxide; cadmium yellow, cadmium red, mercury sulfide and other sulfides or selenides; various sulfates such as barium sulfate and lead sulfate; various silicates such as calcium silicate and ultramarine; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese violet; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder; these metallic flake pigments, mica, flake pigments; metal pigments such as mica, flake pigments, and mica-like iron oxide pigments coated with metal oxides, and pearl pigments; graphite, carbon black, and the like.
Examples of the plastic pigment include "GRANDOLL PP-1000" and "PP-2000S" manufactured by DIC (Co., ltd.).
The pigment to be used may be appropriately selected depending on the purpose, and for example, from the viewpoints of excellent durability, weather resistance and design, it is preferable to use an inorganic oxide such as titanium oxide or zinc white as the white pigment, and carbon black as the black pigment.
The amount of the pigment to be blended is, for example, 1 to 400 parts by mass, and more preferably 10 to 300 parts by mass, in order to improve the adhesion and blocking resistance, based on 100 parts by mass of the total solid content of the polyol composition (X) and the polyisocyanate composition (Y).
(plasticizer)
Examples of the plasticizer include phthalic acid plasticizers, fatty acid plasticizers, aromatic polycarboxylic acid plasticizers, phosphoric acid plasticizers, polyol plasticizers, epoxy plasticizers, polyester plasticizers, and carbonate plasticizers.
Examples of the phthalic acid plasticizer include phthalic acid plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, diheptyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate, ditridecyl phthalate, di-undecyl phthalate, dilauryl phthalate, distearyl phthalate, diphenyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, octyl phthalate, dimethyl isophthalate, di- (2-ethylhexyl) isophthalate, diisooctyl isophthalate, and tetrahydrophthalic acid plasticizers such as tetrahydrophthalic acid di- (2-ethylhexyl) phthalate, di-n-octyl tetrahydrophthalic acid, and diisodecyl tetrahydrophthalic acid.
Examples of the fatty acid plasticizer include adipic acid plasticizers such as di-n-butyl adipate, di- (2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate, di (C6-C10 alkyl) adipate, and di (butyl diglycol) adipate (Japanese text) コ; azelaic acid plasticizers such as di-n-hexyl azelate, di- (2-ethylhexyl) azelate, diisooctyl azelate; sebacic acid plasticizers such as di-n-butyl sebacate, di- (2-ethylhexyl) sebacate, diisononyl sebacate, and the like; maleic acid plasticizers such as dimethyl maleate, diethyl maleate, di-n-butyl maleate, and di- (2-ethylhexyl) maleate; fumaric plasticizers such as di-n-butyl fumarate and di- (2-ethylhexyl) fumarate; itaconic acid plasticizers such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di- (2-ethylhexyl) itaconate; stearic acid plasticizers such as n-butyl stearate, glycerol monostearate, diethylene glycol distearate; oleic plasticizers such as butyl oleate, glycerol monooleate, diethylene glycol monooleate; citric acid plasticizers such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tributyl citrate, acetyl tri- (2-ethylhexyl) citrate, and the like; ricinoleic acid plasticizers such as methyl acetylricinoleate, butyl acetylricinoleate, glycerol monoricinoleate, diethylene glycol monoricinoleate; other fatty acid plasticizers such as diethylene glycol monolaurate, diethylene glycol dipelargonate, pentaerythritol fatty acid ester, and the like.
Examples of the aromatic polycarboxylic acid plasticizer include trimellitic acid plasticizers such as tri-n-hexyl trimellitate, tri- (2-ethylhexyl) trimellitate, tri-n-octyl trimellitate, triisooctyl trimellitate, triisononyl trimellitate, tridecyl trimellitate, triisodecyl trimellitate, and the like; for example, a pyromellitic plasticizer such as tetra- (2-ethylhexyl) pyromellitic acid tetra-n-octyl pyromellitate, and the like.
Examples of the phosphoric acid plasticizer include triethyl phosphate, tributyl phosphate, tris- (2-ethylhexyl) phosphate, tris (butoxyethyl) phosphate, triphenyl phosphate, octadiphenyl phosphate, toluylene phosphate, tris (toluylene) phosphate, tris (xylylene) phosphate, tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, and tris (isopropylphenyl) phosphate.
Examples of the polyol plasticizer include diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol di- (2-ethylbutyrate), triethylene glycol di- (2-ethylhexanoate), and methylenebis (thioglycollic acid) ) Glycol plasticizers such as dibutyl ester; for example, glycerol plasticizers such as monoacetin, triacetin, and tributyrin.
Examples of the epoxy plasticizer include epoxidized soybean oil, butyl epoxystearate, epoxyhexahydrophthalic acid di (2-ethylhexyl), epoxyhexahydrophthalic acid diisodecyl ester, epoxytriglyceride, epoxidized octyl oleate, and epoxidized decyl oleate.
Examples of the polyester plasticizer include adipic acid polyester, sebacic acid polyester, phthalic acid polyester, and the like.
Examples of the carbonate plasticizer include propylene carbonate and ethylene carbonate.
In addition to the plasticizer, a partially hydrogenated terphenyl, an adhesive plasticizer, a polymerizable plasticizer such as diallyl phthalate, an acrylic monomer, or an oligomer, and the like are also included. These plasticizers may be used alone or in combination of 2 or more.
(phosphoric acid compound)
Examples of the phosphoric acid compound include phosphoric acid, pyrophosphoric acid, triphosphoric acid, acid methyl phosphate, acid ethyl phosphate, acid butyl phosphate, dibutyl phosphate, acid 2-ethylhexyl phosphate, bis (2-ethylhexyl) phosphate, acid isododecyl phosphate, acid butoxyethyl phosphate, acid oil phosphate, acid tetracosyl phosphate, 2-hydroxyethyl methacrylate acid phosphate, and polyoxyethylene alkyl ether phosphate.
(form of adhesive)
The adhesive of the present invention may be in any form of a solvent-free type or a solvent-free type, and is particularly suitable for the solvent-free type that the boiling resistance is easily insufficient and the re-dissolution of the printed layer is easily problematic. In the present specification, the "solvent-based" adhesive means a method of applying the adhesive to a substrate, heating the substrate in an oven or the like to volatilize an organic solvent in the coating film, and then bonding the film to another substrate, that is, a so-called dry lamination method. Either one or both of the polyol composition (X) and the polyisocyanate composition (Y) contains an organic solvent capable of dissolving (diluting) the constituent components of the polyol composition (X) and the polyisocyanate composition (Y) used in the present invention.
Examples of the organic solvent include esters such as ethyl acetate, butyl acetate and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and dichloroethane, dimethyl sulfoxide and dimethyl sulfonamide. The organic solvent used as a reaction medium in the production of the constituent components of the polyol composition (X) or the polyisocyanate composition (Y) may be further used as a diluent in the coating.
In the present specification, the "solvent-free type" adhesive means a form of adhesive used in the following method, that is, in the so-called solvent-free lamination method: the polyol composition (X) and the polyisocyanate composition (Y) are substantially free of esters such as ethyl acetate, butyl acetate, cellosolve acetate, and the like, ketones such as acetone, methyl ethyl ketone, isobutyl ketone, cyclohexanone, and the like, ethers such as tetrahydrofuran, dioxane, aromatic hydrocarbons such as toluene, xylene, and the like, halogenated hydrocarbons such as methylene chloride, dichloroethane, and the like, and organic solvents having high solubility such as dimethyl sulfoxide, dimethyl sulfonamide, and particularly ethyl acetate or methyl ethyl ketone, and are bonded to other substrates without a step of evaporating the solvents by heating the adhesive after the adhesive is applied to the substrates with an oven or the like. When the organic solvent used as a reaction medium in the production of the constituent components of the polyol composition (X) or the polyisocyanate composition (Y) and the raw materials thereof is not completely removed and a trace amount of the organic solvent remains in the polyol composition (X) or the polyisocyanate composition (Y), it is understood that the organic solvent is substantially not contained. In addition, in the case where the polyol composition (X) contains a low-molecular-weight alcohol, the low-molecular-weight alcohol reacts with the polyisocyanate composition (Y) to become a part of the coating film, and thus it is not necessary to volatilize it after coating. Therefore, such forms are also handled as solvent-free adhesives, and low molecular weight alcohols are not considered organic solvents.
The adhesive of the present invention is preferably used in such a manner that the ratio [ NCO ]/[ OH ] of the number of moles of isocyanate groups [ NCO ] contained in the polyisocyanate composition (Y) to the number of moles of hydroxyl groups [ OH ] contained in the polyol composition (X) is 1.0 to 3.0. Thus, appropriate curability can be obtained independently of the ambient humidity at the time of application.
< laminate >
The laminate of the present invention is obtained by bonding a plurality of substrates (films or papers) by a dry lamination method or a solvent-free lamination method using the adhesive of the present invention. The film to be used is not particularly limited, and a film corresponding to the purpose may be appropriately selected. Examples of the food packaging film include polyolefin films such as polyethylene terephthalate (PET) films, polystyrene films, polyamide films, polyacrylonitrile films, polyethylene films (LLDPE: low-density polyethylene films, HDPE: high-density polyethylene films), polypropylene films (CPP: unstretched polypropylene films, OPP: biaxially stretched polypropylene films), polyvinyl alcohol films, and ethylene-vinyl alcohol copolymer films.
The film may be a film subjected to a stretching treatment. As a stretching treatment method, a sheet-like resin is usually produced by melt-extruding a resin by an extrusion film-forming method or the like, and then simultaneously biaxially stretching or successively biaxially stretching is performed. In the case of sequential biaxial stretching, it is common to first perform a longitudinal stretching treatment and then perform a transverse stretching treatment. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.
The film surface may be subjected to various surface treatments such as flame treatment and corona discharge treatment as needed to form an adhesive layer free from defects such as film breakage and dishing.
Alternatively, a film in which vapor deposition layers of metal such as aluminum, metal oxide such as silica, and alumina are laminated, and a barrier film containing a gas barrier layer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and vinylidene chloride may be used. By using such a film, a laminate having barrier properties against water vapor, oxygen, alcohol, inert gas, volatile organic compounds (flavor) and the like can be produced.
The paper is not particularly limited, and a known paper base material can be used. Specifically, the paper-making natural fibers such as wood pulp are used and manufactured by a known paper machine, but paper sheets are not particularly limited. Examples of the natural fibers for paper production include wood pulp such as conifer pulp and hardwood pulp, non-wood pulp such as abaca pulp, sisal pulp and flax pulp, and pulp obtained by chemically modifying these pulps. As the kind of pulp, chemical pulp, grinding pulp, chemical grinding pulp, thermomechanical pulp, and the like based on sulfate hydrolysis, acid/neutral/alkali sulfite hydrolysis, sodium salt hydrolysis, and the like can be used. In addition, various commercially available high-quality papers, coated papers, lining papers, impregnated papers, yellow boards, paperboards, and the like can be used.
More specific preferable configurations of the laminate exhibiting the characteristics of the adhesive of the present invention include, but are not limited to, OPP film/adhesive layer/CPP film, OPP film/adhesive layer/LLDPE film, OPP/adhesive layer/aluminum vapor deposited CPP film, PET film/adhesive layer/LLDPE film, PET film/adhesive layer/aluminum vapor deposited CPP film, ny film/adhesive layer/LLDPE film, OPP film/adhesive layer/aluminum vapor deposited PET film/adhesive layer '/LLDPE film, PET film/adhesive layer/aluminum vapor deposited PET film/adhesive layer '/LLDPE film, ny film/adhesive layer/aluminum vapor deposited PET film/adhesive layer '/LLDPE film, and the like. In the above-described configuration, the adhesive layer means a cured coating film of the adhesive of the present invention. The adhesive layer' may be a cured coating film of the adhesive of the present invention, or may be a cured coating film of another adhesive.
The laminate of the present invention may be provided with a print layer between the adhesive layer and the substrate (typically, the substrate that is the outermost layer with respect to the content). The printing layer is formed by a general printing method conventionally used for printing on a film using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink.
When the adhesive of the present invention is a solvent type, the adhesive of the present invention is applied to one substrate by using a roll such as a gravure roll, and the organic solvent is volatilized by heating in an oven or the like, and then the other substrate is bonded to obtain the laminate of the present invention. Preferably, the curing treatment is performed after lamination. The curing temperature is preferably room temperature to 80 ℃, and the curing time is preferably 12 to 240 hours.
When the adhesive of the present invention is solvent-free, a roll such as a coating roll is used to apply the adhesive of the present invention, which is preheated to about 40 to 100 ℃, to one substrate, and then the other substrate is immediately bonded to obtain the laminate of the present invention. Preferably, the curing treatment is performed after lamination. The curing temperature is preferably from room temperature to 70℃and the curing time is preferably from 6 to 240 hours.
The coating amount of the adhesive is appropriately adjusted. In the case of the solvent-type adhesive, the solid content is 1g/m, for example 2 Above and 10g/m 2 Below, preferably 2g/m 2 Above and 5g/m 2 The adjustment is performed in the following manner. In the case of the solvent-free adhesive, for example, the application amount of the adhesive is 1g/m 2 Above and 5g/m 2 Hereinafter, it is preferably 1g/m 2 Above and 3g/m 2 The following is given.
The laminate of the present invention is obtained by bonding 2 substrates with the adhesive of the present invention, but may contain other substrates as required. As a method for laminating the other base material, lamination may be performed by a known method, for example, a dry lamination method, a solvent-free lamination method, a thermal lamination method, a heat sealing method, an extrusion lamination method, or the like. The adhesive used in this case may or may not be the adhesive of the present invention. As the other substrate, the same substrate as the above substrate can be used.
Packaging Material
In the packaging material of the present invention, the laminate is formed into a bag shape and heat-sealed to form a packaging material. As a packaging material, there are various types of packaging materials such as three-side sealed bags, four-side sealed bags, gusset bags, pillow bags, gable-top type bottomed containers, tetra bags, brick-type flexible containers, paper cups, and lidstock. The packaging material of the present invention may be appropriately designed with easy-to-open processing and resealability means.
The packaging material of the present invention can be used industrially as a packaging material for filling foods, lotions and medicines. Specific examples of the use include washing liquid lotions, kitchen liquid lotions, bath liquid soaps, liquid shampoos, liquid conditioners, and pharmaceutical tablets. In addition, the packaging material can also be used for packaging the 2 times of the container.
Examples
The present invention will be described in more detail below with reference to specific examples and examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.
Polyol composition (X)
Synthesis example 1 Synthesis of polyester polyol (A-1)
47.8 parts of diethylene glycol, 3.3 parts of 2-methyl-1, 3-propanediol and 48.9 parts of adipic acid were charged into a glass four-necked flask of 2 liters equipped with stirring blades, a temperature sensor, a nitrogen inlet pipe and a rectifying column. The dehydration reaction was carried out by slowly heating under a nitrogen flow at normal pressure, and the temperature was raised to 220℃and the reaction was continued at 220 ℃. After confirming that the temperature at the top of the rectifying column was 80℃or lower, the rectifying column was removed, and the reactor was switched to a condenser made of glass, and a line was connected from a nitrogen inlet pipe to a vacuum pump, and the condensation reaction was carried out under reduced pressure of 50Torr until a predetermined acid value was reached, thereby obtaining a polyester polyol (A-1). The acid value (mgKOH/g), hydroxyl value (mgKOH/g), designed functional group number and number average molecular weight calculated from the designed functional group number of the polyester polyol (A-1) are shown in Table 1. As polyol composition (X-1), polyester polyol (A-1) was used.
Synthesis examples 2 to 7
Polyester polyols (A-2) to (A-7) were obtained in the same manner as in (Synthesis example 1) except that the raw materials shown in Table 1 were changed. The polyol compositions (X-2) to (X-7) were used. In the table, DEG is diethylene glycol, 2MPD is 2-methyl-1, 3-propanediol, and AA is adipic acid.
TABLE 1
Polyisocyanate composition (Y)
Synthesis example 8 Synthesis of polyester polyol (C' 1-1)
13.3 parts of ethylene glycol, 28.3 parts of 2-methyl-1, 3-propanediol and 58.4 parts of adipic acid were charged into a glass four-necked flask of 2 liters equipped with stirring blades, a temperature sensor, a nitrogen inlet pipe and a rectifying column. The dehydration reaction was carried out by slowly heating under a nitrogen flow at normal pressure, and the temperature was raised to 220℃and the reaction was continued at 220 ℃. After confirming that the temperature at the top of the rectifying column was 80℃or lower, the rectifying column was removed, and the reactor was switched to a condenser made of glass, and a line was connected from a nitrogen inlet pipe to a vacuum pump, and the condensation reaction was performed under reduced pressure of 50Torr until a predetermined acid value was reached, thereby obtaining a polyester polyol (C' 1-1). The acid value (mgKOH/g), hydroxyl value (mgKOH/g), designed functional group number and number average molecular weight calculated from the designed functional group number of the polyester polyol (C' 1-1) are shown in Table 2.
Synthesis examples 9 to 12
Polyester polyols (C '1-2) to (C' 1-5) were obtained in the same manner as in (Synthesis example 8) except that the raw materials shown in Table 2 were changed. In the table, EG is ethylene glycol, 2MPD is 2-methyl-1, 3-propanediol, 3MPD is 3-methyl-1, 5-pentanediol, and AA is adipic acid.
TABLE 2
Synthesis example 13 Synthesis of urethane prepolymer (C-1)
2, 2-diphenylmethane diisocyanate, 2, 4-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate were charged into a glass-made four-necked flask of 2 liters equipped with a stirrer, a thermometer and a nitrogen inlet tube, and the contents of these were 54:45:1 (mass ratio) and 58.3 parts of a mixture heated to 60℃with stirring under a nitrogen stream. 37.5 parts of the polyester polyol (C' 1-1) obtained in example 8 and 4.2 parts of polypropylene glycol having a number average molecular weight of 1000 were added dropwise in several portions, and the mixture was heated and kept at an internal temperature of 70℃for 4 hours to carry out a urethanization reaction, thereby obtaining a urethane prepolymer (C-1) having an NCO group content of 14.5% and isocyanate groups at both ends. This was used as the isocyanate composition (Y-1).
Synthesis examples 14 to 20
Urethane prepolymers (C-2) to (C-8) were obtained in the same manner as in synthesis example 13, except that the compounds and the amounts thereof used in the synthesis were changed to those shown in table 3. The isocyanate compositions (Y-2) to (Y-8) were used.
TABLE 3
TABLE 4
< preparation of adhesive >
Solvent-free adhesives of examples 1 to 9 and comparative examples 1 to 3 were prepared by blending polyol compositions (X-1) to (X-7) and polyisocyanate compositions (Y-1) to (Y-8) heated to 40℃in accordance with tables 5 to 7. The ratio of the diols (a 1) and (c 1) in the table means the ratio (mass%) of the total amount of the diols (a 1) and (c 1) used in the preparation of the adhesive to the total amount of the solid components of the adhesive.
< manufacturing of sample for evaluation >
(production of sample 1 for evaluation)
The coating amount of the film was 1.5g/m on a Ny film (film thickness: 15 μm, width: 600 mm) gravure-printed with a pattern using a printing ink (DIC (strand)), and the film was a film having a film thickness of 1.5g/m 2 The adhesive was applied to the surface of the adhesive, and the surface was bonded to a corona-treated surface of an LLDPE film (film thickness: 60 μm, width: 600 mm), and cured at 40℃for 3 days, to obtain a laminate of Ny/adhesive layer/LLDPE. This was used as sample 1 for evaluation.
(production of sample 2 for evaluation)
An OPP film (film thickness: 20 μm) was gravure-printed with a pattern using a printing ink (FINART, manufactured by DIC (Co., ltd.),600mm wide) at a coating rate of 200 m/min and a coating weight of 1.8g/m 2 The prepared adhesive was applied to the surface of the VMCPP film (film thickness: 25 μm, width: 600 mm), and then the surface was bonded to an aluminum deposition surface of the VMCPP film, to obtain an OPP/adhesive layer/VMCPP laminate. This was used as sample 2 for evaluation.
< evaluation >
(boiling resistance)
Sample 1 for evaluation was cut out so as to be 150mm×300mm, and was folded so that the LLDPE film was inside, and 2 sides of the film were heat-sealed at 1atm and 180℃for 1 second, to prepare a bag. After filling the bag with 1/1/1 sauce (meat sauce: vegetable oil: vinegar=1:1:1), the remaining 1 sides were heat sealed under the same conditions, and the bag was sealed. The bag filled with the content was immersed in hot water at 98℃and subjected to boiling sterilization treatment for 1 hour. The appearance of the pouch after the removal of the contents was observed and evaluated on 3 scales according to the presence or absence of delamination.
Evaluation o: no delamination
Evaluation delta: the layering position is 1-5 parts or less
Evaluation x: the layering part is more than 6
(resolubility of the print layer)
A urethane-based laminating ink (Finart R794 white G3; DIC (manufactured by GmbH)) was adjusted to be based on Cai Enbei #3 manufactured by Cluster Co., ltd. For 15 seconds (25 ℃ C.), was printed on a corona-treated PET (polyethylene terephthalate) film (ESTER film E5102#12) by a gravure press having a plate depth of 43 μm, and was dried or cured by an oven at 70 ℃ to form a printed layer on the PET film.
1g of an adhesive containing the polyol composition (X) and the polyisocyanate composition (Y) was dropped onto the printed matter, and after leaving the mixture in an oven at 50℃for 3 minutes, the portion of the adhesive to be dropped was subjected to a rubbing test with a black cotton swab. The transfer rate of the white ink from the printed matter to the black cotton stick was evaluated, and the results are summarized in tables 5 to 7.
O: less than 0 to 50 percent
×：50％～100％
(laminated appearance)
The deposition surface was visually observed from the OPP film side of the evaluation sample 2 through the printed layer and the adhesive layer, and evaluated according to the following criteria.
And (3) the following materials: pattern without bubbles, unevenness and shaddock surface shape
O: can rarely confirm bubbles, uneven patterns and shaddock surface patterns
X: can clearly confirm the bubbles, uneven patterns and the surface patterns of the grapefruit
(stability over time of polyisocyanate composition (Y))
The polyisocyanate composition (Y) was collected into a transparent glass bottle so as not to enter into bubbles, and after sealing, it was allowed to stand in a desiccator for 3 months. The appearance after storage was observed, and the following evaluation was performed based on the degree of change in turbidity when compared with the appearance before storage, and the results are summarized in table 8.
Evaluation o: no turbidity was observed before and after storage.
Evaluation delta: slightly cloudy after storage.
Evaluation x: haze was generated from the time before storage.
TABLE 5
Example 1 Example 2 Example 3 Example 4 Example 5
Polyester polyol (A-1) 55
Polyester polyol (A-2) 55
Polyester polyol (A-3) 55
Polyester polyol (A-4) 55
Polyester polyol (A-5) 55
Urethane prepolymer (C-1) 100 100 100 100 100
Ratio of diols (a 1) and (c 1) 8.0 9.5 11.1 14.8 18.3
Boiling resistance ○ ○ ○ ○ ○
Resistance to resolubility ○ ○ ○ ○ ○
Laminated appearance ○ ○ ○ ○ ○
TABLE 6
Example 6 Example 7 Example 8 Example 9
Polyester polyol (A-3) 55 55 55 55
Urethane prepolymer (C-3) 100
Urethane prepolymer (C-4) 100
Urethane prepolymer (C-5) 100
Urethane prepolymer (C-6) 100
Ratio of diols (a 1) and (c 1) 11.8 10.2 9.1 11.9
Boiling resistance ○ ○ △ ○
Resistance to resolubility ○ ○ ○ ○
Laminated appearance ○ ◎ ◎ ○
TABLE 7
Comparative example 1 Comparative example 2 Comparative example 3
Polyester polyol (A-1) 55
Polyester polyol (A-6) 55
Polyester polyol (A-7) 55
Urethane prepolymer (C-2) 100
Urethane prepolymer (C-7) 100
Urethane prepolymer (C-8) 100
Ratio of diols (a 1) and (c 1) 0.0 4.6 27.5
Boiling resistance × × ○
Resistance to resolubility ○ ○ ×
Laminated appearance ○ ○ ○
TABLE 8
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Claims (8)

1. A2-liquid curable adhesive comprising a polyol composition X and a polyisocyanate composition Y,
the polyol composition X comprises a polyester polyol A which is the reaction product of a composition comprising a polyvalent alcohol a and a polyvalent carboxylic acid b,
the polyisocyanate composition Y comprises a urethane prepolymer C which is the reaction product of a polyol composition Y comprising a polyester polyol C '1 and an isocyanate compound C '2, the polyester polyol C '1 being the reaction product of a polyvalent alcohol C and a polyvalent carboxylic acid d,
the polyvalent alcohol a contains a diol a1 having only 1 alkyl side chain,
the polyvalent alcohol c contains a diol c1 having only 1 alkyl side chain,
the total amount of the diol a1 and the diol c1 is 5% by mass or more and 20% by mass or less of the total amount of the polyol composition X and the polyisocyanate composition Y.
2. The 2-liquid curable adhesive according to claim 1, wherein the polyvalent alcohol a contains diethylene glycol.
3. The 2-liquid curing adhesive according to claim 1 or 2, wherein the polycarboxylic acid b comprises adipic acid.
4. The 2-liquid curable adhesive according to any one of claims 1 to 3, wherein the polyol composition y contains polyether polyol C'3.
5. The 2-liquid curing adhesive according to any one of claims 1 to 4, wherein the polycarboxylic acid d comprises adipic acid.
6. The 2-liquid curable adhesive according to any one of claims 1 to 5, which is solvent-free.
7. A laminate comprising a first substrate, a second substrate, and an adhesive layer for bonding the first substrate to the second substrate, wherein the adhesive layer is a cured coating film of the 2-liquid curable adhesive according to any one of claims 1 to 6.
8. A packaging material comprising the laminate of claim 7.
CN202280041016.XA 2021-08-05 2022-07-21 Adhesive, laminate, and packaging material Pending CN117460802A (en)

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JPH0481414A (en) * 1990-07-24 1992-03-16 Dainippon Ink & Chem Inc Production of polyurethane resin
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