CN118103472A - Adhesive, laminate, and packaging material - Google Patents

Adhesive, laminate, and packaging material Download PDF

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Publication number
CN118103472A
CN118103472A CN202280069742.2A CN202280069742A CN118103472A CN 118103472 A CN118103472 A CN 118103472A CN 202280069742 A CN202280069742 A CN 202280069742A CN 118103472 A CN118103472 A CN 118103472A
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CN
China
Prior art keywords
film
adhesive
substrate
polyester polyol
acid
Prior art date
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CN202280069742.2A
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Chinese (zh)
Inventor
德永千勇
手岛常行
新居正光
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DIC Corp
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DIC Corp
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Publication of CN118103472A publication Critical patent/CN118103472A/en
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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
    • 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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention provides a two-component curable adhesive, which has a small amount of residual organic solvent in an adhesive coating film and does not have any fear of solvent odor even when a solvent-based adhesive containing a polyester polyol as a main component is used, and a laminate and a packaging material using the adhesive. The present invention provides a two-part curable adhesive comprising a polyester polyol (A), an isocyanate compound (B), an organic solvent (C) and a drying aid (D), a method for producing a laminate using the adhesive, a laminate obtained using the adhesive, and a packaging material produced using the laminate.

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
As packaging materials for foods, medical products, cosmetics, daily necessities, etc., a material in which a metal foil such as an aluminum foil or a metal vapor deposited film is laminated with a plastic film such as polyethylene, polypropylene, vinyl chloride, polyester, nylon in a multilayer manner is used. These laminates are laminated by appropriately combining various plastic films, metal vapor deposited films, or metal foils and bonding them with an adhesive according to the characteristics required for each application. As the adhesive, a two-part curing adhesive containing a polyol composition and a polyisocyanate composition is generally used (for example, patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2018-172492
Disclosure of Invention
Problems to be solved by the invention
A solvent-based adhesive containing a polyester polyol as a main component as in the adhesive described in patent document 1 is excellent in heat resistance and moisture resistance as compared with an adhesive containing a polyether polyol as a main component, but on the other hand, since the polyester polyol has a high affinity with an organic solvent for dilution, the adhesive coating film applied to a substrate has poor solvent release properties, and there is a tendency that the organic solvent is easily left in the adhesive cured coating film. The organic solvent remaining in the adhesive cured coating film may pass through the film to transfer the solvent smell to the content.
The present invention has been made in view of such circumstances, and relates to a two-part curable adhesive, a laminate, and a packaging material, in which the amount of residual organic solvent in an adhesive coating film is small even when a solvent-based adhesive containing a polyester polyol as a main component is used.
Means for solving the problems
The present invention relates to an adhesive, which is a two-part curable adhesive comprising a polyester polyol (a), an isocyanate compound (B), an organic solvent (C) and a drying aid (D), and a laminate and a packaging material each obtained using the adhesive.
Effects of the invention
According to the present invention, a laminate having a small amount of residual organic solvent in a cured coating film of an adhesive can be provided even when a solvent-based adhesive containing a polyester polyol as a main component is used.
Drawings
Fig. 1 is a schematic configuration diagram showing an example of a laminating apparatus used for manufacturing a laminate of the present invention.
Detailed Description
< Adhesive >
The adhesive of the present invention is a two-part curable adhesive comprising a polyester polyol (A), an isocyanate compound (B), an organic solvent (C) and a drying aid (D). The drying aid (D) may be present in the polyol composition (I) together with the polyester polyol (A), or may be prepared separately from the polyol composition (I) and the polyisocyanate composition (II) and used in combination with them immediately before coating. The organic solvent (C) may be contained only in either the polyol composition (I) or the polyisocyanate composition (II), or may be present in both.
(Polyester polyol (A))
The polyester polyol (A) is the reaction product of a monomer composition (A') comprising a polycarboxylic acid and a polyol. Examples of the polycarboxylic acid used for the production of the polyester polyol (a) include: aliphatic polycarboxylic acids such as malonic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, 2-dimethylsuccinic acid, succinic anhydride, alkenylsuccinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic anhydride, itaconic acid, dimer acid, and trimer acid;
Alkyl esters of aliphatic polycarboxylic 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;
Alicyclic polycarboxylic acids such as 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, nadic anhydride (Japanese absolute, chlorobridge anhydride, etc.);
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, diphthalic acid, 1, 2-bis (phenoxy) ethane-p, p' -dicarboxylic acid, benzophenone tetracarboxylic dianhydride, isophthalic acid-5-sodium sulfonate, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, and the like;
Methyl esters of aromatic polycarboxylic acids such as dimethyl terephthalate and dimethyl 2, 6-naphthalate; and the like, 1 kind or 2 or more kinds may be used in combination.
The polyhydric alcohol used for the production of the polyester polyol (a) may be a diol or a polyhydric alcohol having 3 or more functions, and examples of the diol include aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, 1, 3-propanediol, 1, 2-trimethyl-1, 3-propanediol, 2-dimethyl-3-isopropyl-1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 3-methyl-1, 3-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 4-bis (hydroxymethyl) cyclohexane, 2, 4-trimethyl-1, 3-pentanediol, and dimer diol;
Ether diols such as polyoxyethylene glycol and polyoxypropylene glycol;
modified polyether diols obtained by ring-opening polymerization of the above 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 the aliphatic diols with various lactones such as a lactone compound (japanese), epsilon-caprolactone, etc.;
Bisphenol such as bisphenol A and bisphenol F;
Alkylene oxide adducts of bisphenols such as ethylene oxide and propylene oxide, which are obtained by adding ethylene oxide, propylene oxide, and the like to bisphenols such as bisphenol a and bisphenol F.
The above polyol having 3 or more functions may be exemplified by: aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerol, hexanetriol, and pentaerythritol;
Modified polyether polyols obtained by ring-opening polymerization of the above 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 the above aliphatic polyols with various lactones such as epsilon-caprolactone.
The polyester polyol (a) may be a polyester polyurethane polyol (A1) which is obtained by using a polyisocyanate as an essential raw material in addition to the above-mentioned polycarboxylic acid and polyol. Alternatively, the polyester polyol (A) may be a mixture of the polyester polyol (A) and the polyester urethane polyol (A1). The polyisocyanate used for the production of the polyester polyurethane polyol (A1) may be the same as the one exemplified as the isocyanate compound (B) described later, singly or in combination.
The polyester urethane polyol (A1) may be a compound obtained by synthesizing a polyester polyol as a precursor and then elongating the urethane, or may be a compound obtained by reacting a monomer composition containing a polycarboxylic acid, a polyol and a polyisocyanate at one time.
The present invention is more useful when the polyester polyol (a) contains at least one of a polyester polyol (A2) obtained by polycondensing a polyhydric carboxylic acid containing an ortho-oriented aromatic polycarboxylic acid with a polyhydric alcohol, a polyester polyol (A3) having an isocyanurate ring, and a polyester polyol (A4) having a polymerizable carbon-carbon double bond. The adhesive using such a polyester polyol (a) has excellent gas barrier properties, and thus can be produced into a laminate excellent in gas barrier properties, but on the other hand, the evaporation of the organic solvent tends to be easily hindered due to the excellent gas barrier properties. According to the present invention, even such an adhesive can suppress the residue of the organic solvent in the adhesive layer. The polyester polyol (a) may be suitable for many or all of the polyester polyols (A2) to (A4). For example, it may be a reaction product of a monomer composition (A') comprising an ortho-oriented aromatic polycarboxylic acid and a compound having an isocyanurate ring.
As the ortho-oriented aromatic polycarboxylic acid used in the synthesis of the polyester polyol (A2), compounds such as those exemplified above can be used. From the viewpoint of gas barrier properties, the amount of the ortho-oriented aromatic polycarboxylic acid blended in the monomer composition (a') is preferably 20 mass% or more, more preferably 30 mass% or more. The upper limit is not particularly limited, but is, for example, 50 mass% or less.
In the case of using a compound such as the polyester polyol (A2), (A3), or (A4) as the polyester polyol (a), at least 1 selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol is preferably contained as the polyol, and ethylene glycol is more preferably used. By using these polyols, an adhesive having more excellent gas barrier properties can be produced. The amount of these polyols blended in the monomer composition (a') is preferably 5 mass% or more, more preferably 10 mass% or more. The upper limit is not particularly limited, but is, for example, 50 mass% or less.
In the case of using a compound such as the polyester polyol (A2), (A3) or (A4) as the polyester polyol (a), it is also preferable to use a polyol of three or more types such as glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1,2, 4-butanetriol, pentaerythritol, dipentaerythritol, etc. as the polyol. The amount of the tri-or higher polyol to be blended in the monomer composition (A') can be appropriately adjusted, but is preferably 5% by mass, more preferably 10% by mass or more, as an example. The upper limit is not particularly limited, but is 60 mass% or less as an example.
As the compound used when introducing an isocyanurate ring into the polyester polyol (A3), a compound having an isocyanurate ring and 2 or more functional groups capable of reacting with at least one of a carboxyl group and a hydroxyl group in a molecule and having 4 or less carbon atoms of the shortest methylene chain connecting the isocyanurate ring and the functional groups is preferable. If the number of carbon atoms in the methylene chain is greater than 4, the gas barrier property tends to be lowered. The functional groups capable of reacting with at least one of the carboxyl group and the hydroxyl group may be bonded to the isocyanurate ring independently via a methylene chain, or may be a plurality of functional groups bonded to one methylene chain bonded to the isocyanurate ring. The number of carbon atoms of the methylene chain between the functional group closest to the isocyanurate ring and the isocyanurate ring among the plurality of functional groups bonded to one methylene chain may be 4 or less, but the number of carbon atoms of the methylene chain bonded between the plurality of functional groups is preferably 1 or more and 4 or less.
Examples of such a compound include: an amino group-containing isocyanuric acid such as 1,3, 5-tris (aminomethyl) isocyanuric acid, 1,3, 5-tris (2-aminoethyl) isocyanuric acid, 1, 3-bis (2-aminoethyl) -5-methyl-isocyanuric acid, 1, 3-bis (2-aminoethyl) -5-ethyl-isocyanuric acid, 1, 3-bis (2-aminoethyl) -5-propyl-isocyanuric acid, 1, 3-bis (2-aminoethyl) -5-butyl-isocyanuric acid, 1,3, 5-tris (3-aminopropyl) isocyanuric acid, 1, 3-bis (3-aminopropyl) -5-methyl-isocyanuric acid, and the like,
1,3, 5-Tris (hydroxymethyl) isocyanurate, 1, 3-bis (hydroxymethyl) -5-methyl-isocyanurate, 1, 3-bis (hydroxymethyl) -5-ethyl-isocyanurate, 1, 3-bis (hydroxymethyl) -5-butyl-isocyanurate, 1, 3-bis (hydroxymethyl) -5-phenyl-isocyanurate, 1- (hydroxyethyl) -3, 5-bis (hydroxymethyl) -isocyanurate, 1,3, 5-tris (1-hydroxyethyl) isocyanurate, 1, 3-bis (hydroxymethyl) -5- (2-hydroxypropyl) isocyanurate, 1, 3-bis (hydroxymethyl) -5- (2-hydroxy-1-methylpropyl) isocyanurate, 1, 3-bis (hydroxymethyl) -5- (2-hydroxy-2-methylpropyl) isocyanurate, 1,3, 5-tris (2-hydroxyethyl) isocyanurate, 1, 3-bis (2-hydroxyethyl) -5-methyl-isocyanurate, 1, 3-bis (2-hydroxyethyl) -5-ethyl-isocyanurate, 1, 3-bis (2-hydroxyethyl) -5- (1-hydroxyethyl) isocyanurate, hydroxyl-containing isocyanuric acids such as 1,3, 5-tris (3-hydroxypropyl) isocyanuric acid, 1,3, 5-tris (2-hydroxypropyl) isocyanuric acid, 1,3, 5-tris (4-hydroxybutyl) isocyanuric acid, 1,3, 5-tris (3-hydroxybutyl) isocyanuric acid, 1,3, 5-tris (1, 2-hydroxyethyl) isocyanuric acid, 1,3, 5-tris (2, 3-hydroxypropyl) isocyanuric acid, 1, 3-bis (2, 4-hydroxybutyl) -5- (hydroxymethyl) isocyanuric acid, and the like,
Glycidyl group-containing isocyanuric acids such as 1,3, 5-tris (2, 3-epoxypropyl) isocyanuric acid, 1, 3-bis (2, 3-epoxypropyl) -5-methyl-isocyanuric acid, 1, 3-bis (2, 3-epoxypropyl) -5-ethyl-isocyanuric acid, 1, 3-bis (2, 3-epoxypropyl) -5-propyl-isocyanuric acid, and 1,3, 5-tris (3, 4-epoxybutyl) isocyanuric acid,
And isocyanuric acid having a carboxyl group such as 1,3, 5-tris (carboxyl) isocyanuric acid, 1,3, 5-tris (carboxymethyl) isocyanuric acid, 1, 3-bis (carboxymethyl) -5-methyl-isocyanuric acid, 1, 3-bis (carboxymethyl) -5-ethyl-isocyanuric acid, 1, 3-bis (carboxymethyl) -5-butyl-isocyanuric acid, 1, 3-bis (carboxymethyl) -5-phenyl-isocyanuric acid, 1, 3-bis (carboxyethyl) -5-methyl-isocyanuric acid, 1, 3-bis (carboxyethyl) -5-ethyl-isocyanuric acid, 1, 3-bis (carboxypropyl) -5-methyl-isocyanuric acid, 1, 3-bis (carboxyethyl) -5-butyl-isocyanuric acid, 1,3, 5-tris (carboxypropyl) isocyanuric acid, and 1, 3-bis (carboxypropyl) -5-methyl-isocyanuric acid, but not limited thereto. Any one of 1 kind may be used, or 2 or more kinds may be used in combination.
From the viewpoint of gas barrier properties, the proportion of the compound having an isocyanurate ring in the monomer composition (a') is preferably 5% by mass or more, more preferably 10% by mass or more. From the viewpoint of coating suitability, it is preferably 60 mass% or less, more preferably 50 mass% or less.
The number average molecular weight (Mn) of the polyester polyol (a) is not particularly limited, but is, for example, 500 to 100000, more preferably 500 to 50000. The weight average molecular weight (Mw) is, for example, 1000 to 300000, more preferably 2000 to 200000. The number average molecular weight (Mn) and the weight average molecular weight (Mw) in the present specification are values measured by Gel Permeation Chromatography (GPC) under the following conditions.
Measurement device: HLC-8320GPC manufactured by TOSOH Co., ltd
Chromatographic column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by TOSOH Co., ltd
A detector: RI (differential refractometer)
Data processing; multi Station GPC-8020modelII manufactured by TOSOH Co., ltd
Measurement conditions: column temperature 40 DEG C
Solvent tetrahydrofuran
Flow rate 0.35 ml/min
Standard: monodisperse polystyrene
Sample: a solution (100. Mu.l) obtained by filtering a tetrahydrofuran solution having a resin solid content of 0.2% by mass in a microfilter was used
The hydroxyl value of the polyester polyol (A) is preferably in the range of 1 to 350mgKOH/g, more preferably 50mgKOH/g or more and 300mgKOH/g or less. The acid value of the polyester polyol (A) is not particularly limited, but is preferably 10.0mgKOH/g or less. The lower limit is not particularly limited, but is, for example, 0.5mgKOH/g or more. It may be 0mgKOH/g. The hydroxyl value and acid value can be measured by the method described in JIS-K0070.
(Isocyanate Compound (B))
The isocyanate compound (B) may be a known compound having a plurality of isocyanate groups without particular limitation. Examples of the isocyanate compound (B) include: polyisocyanates having an aromatic structure in the molecular structure such as toluene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, triphenylmethane triisocyanate and xylylene diisocyanate, and compounds obtained by modifying part of the NCO groups of these polyisocyanates with a carbodiimide;
Polyisocyanates having an alicyclic structure in the molecular structure such as isophorone diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), 1,3- (isocyanatomethyl) cyclohexane, and the like;
Linear aliphatic polyisocyanates such as 1, 6-hexamethylene diisocyanate, 1, 5-pentamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate, and compounds obtained by modifying part of NCO groups of these polyisocyanates with carbodiimide;
Isocyanurate bodies of these polyisocyanates; allophanate bodies of these polyisocyanates; biuret bodies of these polyisocyanates; adducts of these polyisocyanates modified with trimethylolpropane; polyurethane polyisocyanates which are the reaction products of these polyisocyanates with polyols, and the like.
When a polyurethane polyisocyanate is used as the isocyanate compound (B), a polyurethane polyisocyanate obtained by reacting the above polyisocyanate and polyol in such a ratio that the equivalent ratio of isocyanate groups to hydroxyl groups [ NCO ]/[ OH ] is 1.5 to 5.0 is preferable from the viewpoint of balance of cohesive force and flexibility of the adhesive coating film.
As the polyol used in the preparation of the polyurethane polyisocyanate, the same polyols as those exemplified as the raw material of the polyester polyol (a) can be used.
From the viewpoint of obtaining good gas barrier properties, the isocyanate compound (B) is preferably an isocyanate having an aromatic ring or a derivative (B1) thereof. Specific examples of the isocyanate compound (B1) include isocyanate compounds having a skeleton derived from xylylene diisocyanate, hydrogenated xylylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate.
From the viewpoint of obtaining good gas barrier properties, the isocyanate compound (B) is also preferably a polyurethane polyisocyanate (B2) obtained by reacting at least one selected from the polyester polyols (A2), (A3) and (A4) with an isocyanate having an aromatic ring or its derivative (B1) in such a ratio that the equivalent ratio of isocyanate groups to hydroxyl groups [ NCO ]/[ OH ] is 1.5 to 5.0.
(Organic solvent (C))
The adhesive of the present invention contains an organic solvent (C) capable of diluting (dissolving) the polyester polyol (A). Examples of the organic solvent (C) 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 (I) or the polyisocyanate composition (II) may be further used as a diluent in the coating. The present invention is particularly effective when the organic solvent (C) is an ester such as ethyl acetate.
(Drying aid (D))
The drying aid (D) has a function of promoting volatilization of the organic solvent (C). Examples of the drying aid (D) include isosorbide, isomannide, and 1,4:3, 6-dianhydro-L-iditol, triacetin, etc. Preferably isosorbide is used. By including the drying aid (D), the organic solvent (C) is easily volatilized in the drying step, and the organic solvent (C) is less likely to remain in the cured coating film of the adhesive.
The drying aid (D) preferably has a hydroxyl group. Thus, the isocyanate compound (B) reacts with the isocyanate compound (B) and is incorporated into the cured coating film, and therefore, unlike the additive having no functional group, there is no fear of transferring from the adhesive layer to another layer with the lapse of time, and the influence on the physical properties of the adhesive layer with the lapse of time is small. The drying step here refers to a step of mixing the polyol composition (I) and the polyisocyanate composition (II) and applying the mixture to a substrate, and then passing the mixture through an oven to volatilize the organic solvent (C) contained in the adhesive coating film.
The hydroxyl group of the drying aid (D) is preferably a secondary hydroxyl group. Since the reactivity with the isocyanate compound (B) is lower than that of the primary hydroxyl group, the reaction with the isocyanate compound (B) before reaching the drying step can be effectively suppressed.
The blending amount of the drying aid (D) is preferably 0.5 mass% or more, more preferably 1 mass% or more of the total solid content of the adhesive, from the viewpoint of effectively suppressing the residue of the organic solvent (C). From the viewpoint of the solubility of the drying aid (D) in the binder solution, it is preferably 50 mass% or less, more preferably 30 mass% or less.
(Other component of adhesive)
The adhesive of the present invention may contain components other than the above components. These components may be contained in either or both of the polyol composition (I) and the polyisocyanate composition (II), or may be prepared separately therefrom and used in combination immediately before the application of the adhesive. The components are described below.
(Polyol (E))
The polyol composition (I) may contain a polyol (E) other than the polyester polyol (A). Examples of the polyol (E) include polyols exemplified as the polyol used for the production of the polyester polyol (A). When the polyol composition (I) contains the polyol (E), the amount to be blended is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or more, relative to 100 parts by mass of the total amount of the polyester polyol (a) and the polyol (E).
(Catalyst (F))
The adhesive of the present invention can promote the curing reaction by using the catalyst (F) as needed. The catalyst (F) is not particularly limited as long as it promotes the urethanization reaction of the polyol composition (I) and the polyisocyanate composition (II), and examples thereof include metal catalysts, amine catalysts, aliphatic cyclic amide compounds, and titanium chelate complexes.
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, zirconium acetylacetonate, and the like. From the viewpoints of toxicity and catalytic activity, iron acetylacetonate (Fe (acac) 3) or manganese acetylacetonate (Mn (acac) 2) is preferable.
Examples of the inorganic metal catalyst include a catalyst 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, and zinc naphthenate, organotin diacetate, stannous dioctanoate, stannous dioleate, stannous dilaurate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, and 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, and titanium compounds such as tetraisopropoxytitanium, dibutyltitanium dichloride, tetrabutyltitanate, and titanium butoxide trichloride.
Examples of the amine-based catalyst include triethylenediamine, 2-methyltriethylenediamine, quinine (quinidine), 2-methylquinine, 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. Among them, epsilon caprolactam is more effective in promoting cure.
The titanium chelate complex is a compound whose catalytic activity can be improved by ultraviolet irradiation, and is preferably a titanium chelate complex having an aliphatic diketone or an aromatic diketone as a ligand, in view of excellent curing acceleration effect. In the present invention, a titanium chelate complex having an alcohol having 2 to 10 carbon atoms as a ligand in addition to an aromatic diketone or an aliphatic diketone is preferable from the viewpoint that the effect of the present invention is more remarkable.
The catalyst (F) may be used alone or in combination of 2 or more. The amount of the catalyst (F) to be blended is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 2 parts by mass, based on 100 parts by mass of the total solid content of the polyol composition (I) and the polyisocyanate composition (II).
(Pigment (G))
The adhesive of the present invention may contain a pigment (G) as required. The pigment (G) to be used is not particularly limited, and examples thereof include 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 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 (quartz 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 (bordeaux) 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 bright red B (Cinquasia Red B); various dioxazine pigments such as dioxazine violet; various condensed azo pigments such as solid penetration (Cromophtal); nigrosine, etc.
Examples of the inorganic pigment include various chromates such as chrome yellow, zinc chromate, and molybdenum orange; various ferric cyanide compounds such as Prussian blue; various metal oxides such as titanium oxide, zinc oxide, mar Pi Kehuang (mapico yellow), iron oxide red, 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 pearlescent pigments; graphite, carbon black, and the like.
Examples of the plastic pigment include "GRANDOLL PP-1000" manufactured by DIC, inc., and "PP-2000S".
The pigment (G) 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 oxide as a white pigment, and carbon black as a black pigment.
The amount of the pigment (G) 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, relative to 100 parts by mass of the total solid content of the polyol composition (I) and the polyisocyanate composition (II).
(Adhesion promoter (H))
The adhesive of the present invention may contain an adhesion promoter (H). Examples of the adhesion promoter (H) include coupling agents such as silane coupling agents, titanate coupling agents, and aluminum coupling agents, and epoxy resins.
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 tetrastearyloxytitanium.
Examples of the aluminum-based coupling agent include aluminum acetoacetoxy diisopropoxide.
Examples of the epoxy resin include epoxy resins such as Epi-Bis type, novolac type, beta-methyl epichlorohydrin (Japanese text: beta-phenolic), cyclic ethylene oxide type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, polycarboxylic acid ester type, amino glycidyl type, resorcinol type, triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, acrylic acid diglycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, p-t-butylphenyl glycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, methacrylic acid diglycidyl ether, butyl glycidyl ether, and the like, which are generally commercially available.
The adhesive of the present invention may contain phosphoric acid (I). Examples of the phosphoric acid (I) 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. When the adhesive of the present invention contains the phosphoric acid (I), the amount to be blended is preferably 1ppm to 200ppm based on the total amount of the solid components of the adhesive.
(Other additives)
The adhesive of the present invention may contain, in addition to the above-mentioned components, inorganic fine particles such as leveling agents, colloidal silica and alumina sol, polymethyl methacrylate-based organic fine particles, defoamers, anti-sagging agents, wetting dispersants, viscosity modifiers, ultraviolet absorbers, metal deactivators, peroxide decomposers, flame retardants, reinforcing agents, plasticizers, lubricants, rust inhibitors, fluorescent brighteners, inorganic heat ray absorbers, flame retardants, antistatic agents, dehydrating agents, thermoplastic elastomers conventionally known, tackifiers, melamine resins, reactive elastomers, and the like. The amount of these additives may be appropriately adjusted within a range not impairing the desired adhesive of the present invention.
(Amount of blending)
The polyol composition (I) and the polyisocyanate composition (II) are preferably used after being adjusted so that the molar ratio ([ NCO ]/[ OH ]) of the isocyanate groups contained in the polyisocyanate composition (II) to the hydroxyl groups contained in the polyol composition (I) is 0.3 to 6.
< Method for producing laminate >
Next, a method for producing the laminate of the present invention will be described. Fig. 1 is a schematic configuration diagram showing an example of a laminating apparatus 10 used for manufacturing a laminate of the present invention. The laminating apparatus 10 includes film supply apparatuses 1 and 2, a coating apparatus 3, a drying apparatus 4, a bonding apparatus 5, and a winding apparatus 6. The first substrate W1 is placed on the winding roller R1, and the second substrate W2 is placed on the winding roller R2.
The coating apparatus 3 is an apparatus for applying an adhesive to the 1 st substrate W1. The coating apparatus 3 includes, as an example, an adhesive transfer roller 3a, an impression cylinder 3b, an adhesive tank 3c, a squeegee 3d, and a smoothing roller 3e. Instead of the adhesive groove 3c and the squeegee 3d, a sealing squeegee may be used. The adhesive G entering the adhesive groove 3c is transferred to the 1 st substrate W1 via the adhesive transfer roller 3 a. At this time, the surplus adhesive G adhering to the adhesive transfer roller 3a is scraped off by the scraper 3 d. The impression cylinder 3b is a rotating body for winding the 1 st substrate W1 and pressurizing the same with the adhesive transfer roller 3a to adhere the adhesive G adhering to the adhesive transfer roller 3a to the 1 st substrate W1. The smoothing roller 3e is a rotating body that smoothes the application surface of the adhesive G transferred to the 1 st substrate W1, and rotates in a direction opposite to the film advancing direction.
The transport speeds of the 1 st substrate W1 and the 2 nd substrate W2 are arbitrarily set, and are, for example, 80m/min to 300 m/min. Preferably 100m/min or more, more preferably 150m/min or more, and preferably 250m/min or less, more preferably 200m/min or less.
The adhesive G entering the adhesive groove 3C is the adhesive described above, and is an adhesive in which a two-part adhesive including the polyester polyol (a), the isocyanate compound (B), the organic solvent (C) and the drying aid (D) is mixed. By including the drying aid (D) in the adhesive G, a laminate in which the residual amount of the organic solvent (C) in the adhesive layer to be described later is greatly reduced can be obtained.
The amount of the adhesive G applied can be appropriately adjusted, and as an example, the amount of the solid component is 1G/m 2 to 10G/m 2, preferably 1G/m 2 to 5G/m 2.
Next, the 1 st substrate W1 is transported to the drying device 4. The drying device 4 is a device for evaporating the organic solvent (C) in the adhesive transferred to the 1 st substrate W1 by heating. As the heating method, a hot air blowing method is widely used. The drying apparatus 4 is generally provided with a plurality of drying ovens. When the drying apparatus 4 includes a plurality of drying ovens, the respective drying ovens may be set to the same temperature or to different temperatures.
When a plurality of drying ovens are provided and each of the temperatures is set to be different, it is preferable that the temperature of the drying oven be gradually increased from the drying oven located on the upstream side with respect to the transport direction of the 1 st substrate W1 to the drying oven located on the downstream side. The temperature of the drying furnace is preferably 50 ℃ or more and 100 ℃ or less.
The 1 st substrate W1 passing through the drying device 4 is transported to the bonding device 5, and bonded to the 2 nd substrate W2 via the adhesive G. The bonding apparatus 5 includes a pair of nip rollers 5a and 5b, and bonds the 1 st substrate W1 and the 2 nd substrate W2 under pressure between the nip rollers 5a and 5b. The pinch roller 5a is a rubber roller, and the pinch roller 5b is a metal roller. The grip roller 5b is provided with a heating device, not shown, for adjusting the temperature of the adhesive G. The laminate W3 bonded by the nip rollers 5a and 5b is sent to the winding device 6 via the cooling roller 5 c.
The bonding device 5 may further include a cooling roller 5c. The cooling roller 5c is disposed between the nip rollers 5a and 5b and the winding device 6, and includes a mechanism for cooling the rollers. The cooling means may be a method of introducing water into the roller. After the laminate W3 is cooled by the cooling roller 5c, the laminate is wound up by applying tension by the winding device 6. This prevents winding up and curling of the laminate W3. The wound laminate W3 is cured at room temperature to 80 ℃ for 12 to 240 hours to obtain the laminate of the present invention.
< Laminate >
The laminate of the present invention is obtained by bonding a plurality of films or papers by a dry lamination method using the adhesive of the present invention. The film to be used is not particularly limited, and a film corresponding to the application can be appropriately selected. Examples of the food packaging film include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film, MDOPE: uniaxially stretched polyethylene film, OPE: biaxially stretched polyethylene film), polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), polyolefin film such as gas barrier heat seal film having an olefin heat seal resin layer provided on one or both sides of a resin having gas barrier properties such as ethylene vinyl alcohol copolymer and polyvinyl alcohol, polyvinyl alcohol film, ethylene vinyl alcohol copolymer film, and the like.
In addition, a biomass film formed of a material containing a biomass-derived component is also preferably used. For example, sheets such as those listed in a list of biomass-approved goods recorded by the japan organic resource society of general financial law may be used in addition to the sales of the biomass membranes by the companies.
Specifically, as a widely known biomass film, a biomass film using biomass-derived ethylene glycol as a raw material is exemplified. The biomass-derived ethylene glycol is ethylene glycol produced from ethanol (biomass ethanol) produced from biomass. For example, biomass-derived ethylene glycol can be obtained by a conventionally known method, such as a method of producing ethylene glycol via ethylene oxide, with respect to biomass ethanol. In addition, a commercially available biomass ethylene glycol may be used, and for example, a biomass ethylene glycol sold by India Glycols company may be suitably used.
For example, as an alternative to conventional polyethylene terephthalate films using petroleum-based materials, films containing biomass polyesters, biomass polyethylene terephthalate, and the like, in which biomass-derived ethylene glycol is used as a diol unit and fossil-fuel-derived dicarboxylic acid is used as a dicarboxylic acid unit, are known.
The dicarboxylic acid units of biomass polyesters use dicarboxylic acids of fossil fuel origin. As the dicarboxylic acid, an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, and derivatives thereof can be used without limitation.
In addition, the copolymer polyester may be obtained by adding a copolymerization component to the polyester as a 3 rd component selected from at least 1 type of polyfunctional compounds among 2-functional hydroxycarboxylic acids, 3-functional or higher polyols for forming a crosslinked structure, 3-functional or higher polycarboxylic acids and/or anhydrides thereof, and 3-functional or higher hydroxycarboxylic acids, in addition to the diol component and the dicarboxylic acid component.
For example, as an alternative to a conventional polyolefin film using a petroleum-based raw material, a biomass polyolefin film such as a biomass polyethylene film or a biomass polyethylene-polypropylene film containing a polyethylene resin derived from biomass glycol is also known.
The polyethylene resin is not particularly limited except that the biomass-derived ethylene glycol is used as a part of the raw material, and examples thereof include homopolymers of ethylene, copolymers of ethylene and α -olefin (ethylene- α -olefin copolymers containing 90 mass% or more of ethylene units) of which main component are ethylene, and the like, and 1 kind of the above-mentioned copolymers may be used alone or 2 kinds or more may be used in combination.
The α -olefin constituting the copolymer of ethylene and α -olefin is not particularly limited, and examples thereof include α -olefins having 4 to 8 carbon atoms such as 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. Known polyethylene resins such as low-density polyethylene resins, medium-density polyethylene resins and linear low-density polyethylene resins can be used. Among them, linear low density polyethylene resins (LLDPE) (copolymer of ethylene and 1-hexene or copolymer of ethylene and 1-octene) are preferable, and linear low density polyethylene resins having a density of 0.910 to 0.925g/cm 3 are more preferable, from the viewpoint that even when friction occurs between films, damage such as open pores and breakage is less likely to occur.
As the biomass film, a biomass film using a biomass raw material having a degree of biomass plastics different from that specified in ISO16620 or astm d6866 is also in circulation. In the atmosphere, there is 1 radioactive carbon 14C in 1012, and this ratio does not change in the carbon dioxide in the atmosphere, and thus in the plant in which the carbon dioxide is immobilized by photosynthesis, this ratio does not change. Therefore, the radioactive carbon 14C is contained in the carbon of the plant-derived resin. In contrast, the radioactive carbon 14C is hardly contained in the carbon of the fossil fuel-derived resin. Therefore, the concentration of the radioactive carbon 14C in the resin is measured by an accelerator mass spectrometer, whereby the content of the plant-derived resin in the resin, that is, the biomass plasticity can be obtained.
Examples of the plant-derived low-density polyethylene having a biomass plastics content of 80% or more, preferably 90% or more, which is specified in ISO16620 or ASTM D6866, include trade names "SBC818", "SPB608", "SBF0323HC", "STN7006", "SEB853", and "SPB681" manufactured by Braskem corporation, and films using these as raw materials can be suitably used.
Films and sheets containing starch and polylactic acid as biomass materials are also known. They can be appropriately selected and used according to the purpose.
The biomass film may be a laminate of a plurality of biomass films, or may be a laminate of a conventional petroleum-based film and a biomass film. These biomass films may be unstretched films or stretched films, and the production method thereof is not limited.
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, 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. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.
In order to form an adhesive layer free from defects such as film breakage and shrinkage cavity, the film surface may be subjected to various surface treatments such as flame treatment and corona discharge treatment, as necessary.
Alternatively, a film having a vapor deposition layer of a metal such as aluminum, silica, or alumina, or a barrier film having a gas barrier layer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, or vinylidene chloride may be used in combination. By using such a film, a laminate having barrier properties against water vapor, oxygen, alcohol, inert gas, volatile organic compounds (aroma) 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 fiber such as wood pulp is used and manufactured by a known paper machine, and the paper-making sheet is 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, cardboard, paperboard, and the like can be used.
More specific laminate structures include:
(1) Substrate 1/adhesive layer 1/sealing film
(2) Substrate 1/adhesive layer 1/metal vapor deposited unstretched film
(3) Substrate 1/adhesive layer 1/metal vapor deposited stretched film
(4) Transparent vapor deposition stretched film/adhesive layer 1/sealing film
(5) Substrate 1/adhesive layer 1/substrate 2/adhesive layer 2/sealing film
(6) Substrate 1/adhesive layer 1/metal vapor deposition stretched film/adhesive layer 2/sealing film
(7) Substrate 1/adhesive layer 1/transparent vapor deposition stretched film/adhesive layer 2/sealing film
(8) Substrate 1/adhesive layer 1/metal layer/adhesive layer 2/sealing film
(9) Substrate 1/adhesive layer 1/substrate 2/adhesive layer 2/metal layer/adhesive layer 3/sealing film
(10) Substrate 1/adhesive layer 1/metal layer/adhesive layer 2/substrate 2/adhesive layer 3/sealing film, etc., but is not limited thereto.
Examples of the substrate 1 used in the constitution (1) include MDOPE film, OPE film, OPP film, PET film, nylon film, paper, and the like. As the base material 1, a material coated for the purpose of improving gas barrier properties, ink receptivity when a print layer to be described later is provided, and the like may be used. Examples of the commercial products of the substrate film 1 obtained by coating include K-OPP film and K-PET film. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of the sealing film include a CPP film, an LLDPE film, and a gas barrier heat sealing film. A print layer may be provided on the surface of the substrate 1 on the adhesive layer 1 side (the surface of the coating layer on the adhesive layer 1 side in the case of using a material obtained by coating as the substrate film 1) or on the surface opposite to the adhesive layer 1. The printing layer is formed by a usual printing method for printing a polymer film or paper using various printing inks such as gravure ink, flexo ink, offset ink, stencil ink, and inkjet ink.
Examples of the substrate 1 used in the structures (2) and (3) include MDOPE films, OPE films, OPP films, PET films, papers, and the like. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. As the metal vapor deposited unstretched film, a VM-CPP film, a VM-LLDPE film, or the like obtained by metal vapor deposition of aluminum or the like on a CPP film, a LLDPE film, or a gas barrier heat seal film can be used, and as the metal vapor deposited stretched film, a VM-MDOPE film, a VM-OPE film, or a VM-OPP film obtained by metal vapor deposition of aluminum or the like on a MDOPE film, an OPE film, or an OPP film can be used. A print layer may be provided on either side of the base material 1 as in the case of the configuration (1).
Examples of the transparent vapor-deposited stretched film used in the constitution (4) include a film obtained by vapor-depositing silica or alumina on MDOPE film, OPE film, OPP film, PET film, nylon film, or the like. A film obtained by applying a coating to a deposition layer for the purpose of protecting an inorganic deposition layer of silica or alumina may be used. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. The sealing film may be the same as the sealing film of the constitution (1). A print layer may be provided on the adhesive layer 1 side surface of the transparent vapor-deposited stretched film (when a material obtained by coating an inorganic vapor-deposited layer is used, the adhesive layer 1 side surface of the coating layer). The method for forming the printed layer is the same as the constitution (1).
The substrate 1 used in the constitution (5) may be a PET film, paper, or the like. The substrate 2 may be a nylon film or the like. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. The sealing film may be the same as the sealing film of the constitution (1). A print layer may be provided on either side of the substrate 1 as in the case of the configuration (1).
The substrate 1 of the constitution (6) is the same as the substrates of the constitution (2) and (3). Examples of the metal vapor deposition stretched film include a VM-MDOPE film, a VM-OPE film, a VM-OPP film, and a VM-PET film obtained by vapor deposition of metal such as aluminum on MDOPE film, OPE film, OPP film, and PET film. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. The sealing film may be the same as the sealing film of the constitution (1). A print layer may be provided on either side of the substrate 1 as in the case of the configuration (1).
The substrate 1 constituting (7) may be a PET film, paper, or the like. The transparent vapor deposition stretched film may be the same as the composition (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. The sealing film may be the same as the sealing film of the constitution (1). A print layer may be provided on either side of the substrate 1 as in the case of the configuration (1).
The substrate 1 constituting (8) may be a PET film, paper, or the like. Examples of the metal layer include aluminum foil. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. The sealing film may be the same as the sealing film of the constitution (1). A print layer may be provided on either side of the substrate 1 as in the case of the configuration (1).
The base material 1 constituting (9) and (10) includes PET film, paper, and the like. The substrate 2 may be a nylon film or the like. Examples of the metal layer include aluminum foil. At least one of the adhesive layers 1, 2, 3 is a cured coating film of the adhesive of the present invention. The sealing film may be the same as the sealing film of the constitution (1). A print layer may be provided on either side of the substrate 1 as in the case of the configuration (1).
When the laminate of the present invention contains at least one of a metal deposition layer, a transparent deposition layer, and a metal layer, the adhesive layer in contact with the metal deposition layer, the transparent deposition layer, and the metal layer is preferably a cured coating film of the adhesive of the present invention.
When the adhesive of the present invention is used as an adhesion auxiliary agent, the adhesive auxiliary agent of the present invention is roll-coated with a film material to be a base material using a gravure roll or the like, the organic solvent is volatilized by heating in an oven or the like, and then the melted polymer material is laminated by an extruder, whereby the laminate of the present invention is obtained.
The laminate of the present invention may further comprise other films and substrates in addition to the above-described structures (1) to (10). As other substrates, porous substrates such as paper, wood, leather and the like described later may be used in addition to the stretched film, the unstretched film and the transparent vapor-deposited film. The adhesive used for bonding other substrates may or may not be the adhesive of the present invention.
Among them, the present invention is useful when the base material to which the adhesive is applied is an olefin film such as a polyethylene film or a polypropylene film. In general, when a solvent-based adhesive containing a polyester polyol as a main component is applied to an olefin film, an organic solvent tends to remain in the adhesive coating film as compared with the case of applying the adhesive to a substrate other than the olefin film. However, according to the adhesive of the present invention, even when such an adhesive is applied to an olefin film, the amount of the remaining organic solvent can be reduced, and a laminate having a small solvent odor can be provided.
More specific examples of the composition include an OPE film/adhesive layer/LLDPE film, MDOPE film/adhesive layer/LLDPE film, OPP film/adhesive layer/CPP film, OPP film/adhesive layer/LLDPE film, OPE film/adhesive layer/CPP film, MDOPE film/adhesive layer/CPP film, and the like. In these structures, an aluminum deposition layer may be provided on the surface of the LLDPE film or CPP film on the adhesive layer side (VMCPP film or VMLLDPE film).
Or may be OPP film/adhesive layer/VM-OPP film/adhesive layer/CPP film, OPP film/adhesive layer/OPP-VM film/adhesive layer/CPP film, OPP film/adhesive layer/VM-OPP film/adhesive layer/VMCPP film, OPP film/adhesive layer/OPP-VM film/adhesive layer/VMCPP film, OPP film/adhesive layer/VM-OPP film/adhesive layer/LLDPE film, OPP film/adhesive layer/OPP-VM film/adhesive layer/LLDPE film, OPP film/adhesive layer/VM-OPP film/adhesive layer/VMLLDPE film, OPP film/adhesive layer/OPP-VM film/adhesive layer/VMLLDPE film, or the like. The LLDPE film may be a transparent film or a white colored film.
Or an OPP film/adhesive layer/VM-OPP film/heat seal layer (layer coated with heat seal agent), an OPP-VM film/adhesive layer/CPP film, an OPP-VM film/adhesive layer/VMCPP film, or the like.
In these configuration examples, the term "VM-OPP film/adhesive layer/CPP film" means that the aluminum vapor deposition layer is located on the surface of the OPP film opposite to the CPP film, and the term "OPP-VM film/adhesive layer/CPP film" means that the aluminum vapor deposition layer is located on the surface of the OPP film on the CPP film side. The same applies to the following. In these configuration examples, a print layer may be provided on any surface of the film that is the outermost layer when viewed from the content.
The present invention is also useful when a printed layer is provided on the surface to which the adhesive is applied. When a solvent-based adhesive containing a polyester polyol is applied to a print layer, an organic solvent tends to remain in the adhesive layer as compared with when the adhesive is applied to a substrate on which no print layer is provided. However, according to the present invention, even when such an adhesive is applied to a print layer, the amount of remaining organic solvent can be reduced, and a laminate having a small solvent odor can be provided.
The "other layer" may contain known additives, stabilizers, such as antistatic agents, easy-to-adhere coating agents, plasticizers, lubricants, antioxidants, and the like. The "other layer" may be a layer obtained by subjecting the surface of the film to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, or the like as a pretreatment in order to improve adhesion when laminated with other materials.
The laminate of the present invention can be suitably used for various purposes, for example: packaging materials for foods, pharmaceuticals, living goods, paper tableware such as a cover, paper straw, paper towel, paper spoon, paper tray, paper cup, etc., barrier wall material, roof material, solar cell panel material, packaging material for batteries, window material, outdoor flooring material, lighting protection material, automobile member, advertisement board, poster, etc., decorative sheet used in injection molding and decoration method, packaging material for washing liquid lotion, kitchen liquid lotion, bath liquid soap, liquid shampoo, liquid hair conditioner, etc., etc.
< Packaging Material >
The laminate of the present invention can be used as a multilayer packaging material for the purpose of protecting foods, medicines, and the like. When used as a multilayer packaging material, the layer composition can be changed according to the content, the environment of use, and the form of use. In addition, an easy-to-open processing and resealing mechanism may be appropriately provided for the package of the present invention.
The packaging material of the present invention is obtained by using the laminate of the present invention, laminating the surfaces of the sealing films of the laminate so as to face each other, and heat-sealing the peripheral ends thereof into a bag shape. Examples of the bag-making method include a method of heat-sealing the peripheral end portion of the laminate of the present invention in a form of, for example, a side seal type, a two-side seal type, a three-side seal type, a four-side seal type, an envelope type, a palm type, a pleated type, a flat bottom type, a square bottom type, a three-dimensional bag (gusset) type, or other heat-seal type by folding or overlapping the laminate so that the surfaces of the inner layers (surfaces of the seal films) face each other. The packaging material of the present invention can take various forms depending on the content, the environment of use, and the form of use. The packaging material may be a self-supporting packaging material (self-supporting bag). The heat-sealing method may be performed by a known method such as bar sealing, rotary roll sealing, tape sealing, instantaneous sealing, high-frequency sealing, or ultrasonic sealing.
The packaging material of the present invention is filled with the content from the opening portion thereof, and then the opening portion is heat-sealed to produce a product using the packaging material of the present invention. Examples of the filled content include food products: snack foods such as rice cake, bean, nut, biscuit, wafer, marshmallow, pie, half-cooked cake, candy, and snack; main foods such as bread, instant noodles, dried noodles, pasta, sterilized packaged rice, japanese braised rice, porridge, packaged rice cake, and oatmeal; farm products such as pickles, boiled beans, natto, miso, frozen bean curd, lentinus Edodes, rhizoma Amorphophalli, processed food of mountain vegetable, jam, peanut butter, salad, frozen vegetables, and processed food of potato; animal products such as ham, bacon, sausage, chicken processed product, and salted beef; fish ham/sausage, minced fish, fish plate, sea weed, dried bonito, salted fish, smoked salmon, and marine processed product such as peppery walleye pollack; pulp such as peach, orange, pineapple, apple, pear, cherry, etc.; vegetables such as corn, asparagus, mushroom, onion, carrot, white radish, and potato; cooked food such as frozen side dish and refrigerated side dish represented by hamburger, meat ball, fried seafood, dumpling, cola cake, etc.; cream, margarine, cheese, fresh cream, instant creamer, infant formula and other milk products; liquid seasonings, instant curry, pet food, and the like.
In addition, the product can be used as a non-food product, and also can be used as various packaging materials for cigarettes, disposable body warmer, medical supplies such as infusion bags, washing liquid lotion, kitchen liquid lotion, bath liquid soap, liquid shampoo, liquid conditioner, cosmetics such as cosmetic water and emulsion, vacuum heat insulating material, battery, and the like.
Examples
The present invention will be described in more detail with reference to specific examples and examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" are "parts by mass" and "% by mass", respectively, unless otherwise specified.
< Synthesis of polyester polyol (A) >
Synthesis example 1 Synthesis of polyester polyol (A-1)
To a polyester reaction vessel equipped with a stirrer, a nitrogen inlet pipe, a schner pipe, and a condenser, 20.98 parts of ethylene glycol, 0.12 parts of glycerin, 50.94 parts of 1,3, 5-tris (2-hydroxyethyl) isocyanurate, and 50.41 parts of phthalic anhydride were added, and the mixture was heated slowly so that the upper temperature of the rectifying pipe was not higher than 100℃and the internal temperature was kept at 220 ℃. The esterification reaction was terminated at an acid value of 1mgKOH/g or less to obtain a polyester polyol (A-1) having a number average molecular weight of 670. The hydroxyl value was 230.2mgKOH/g.
Synthesis example 2 Synthesis of polyester polyol (A-2)
48.56 Parts of ethylene glycol, 0.12 part of glycerin, 16.54 parts of 1,3, 5-tris (2-hydroxyethyl) isocyanurate and 66.88 parts of phthalic anhydride were added to a polyester reaction vessel equipped with a stirrer, a nitrogen inlet pipe, a Snyder pipe and a condenser, and the mixture was heated slowly so that the upper temperature of the rectifying pipe was not higher than 100℃and the internal temperature was kept at 220 ℃. After the esterification reaction was completed at an acid value of 1mgKOH/g or less, 0.015 parts of phosphoric acid was added to obtain a polyester polyol (A-2) having a number average molecular weight of 335. The hydroxyl value was 360.0mgKOH/g.
Synthesis example 3 Synthesis of polyester polyol (A-3)
To a polyester reaction vessel equipped with a stirrer, a nitrogen inlet pipe, a schner pipe, and a condenser, 28.98 parts of ethylene glycol, 0.16 parts of glycerin, 84.56 parts of 1,3, 5-tris (2-hydroxyethyl) isocyanurate, and 57.54 parts of phthalic anhydride were added, and the mixture was heated slowly so that the upper temperature of the rectifying pipe was not higher than 100 ℃ and the internal temperature was kept at 220 ℃. The esterification reaction was terminated at an acid value of 1mgKOH/g or less to obtain a polyester polyol (A-3) having a number average molecular weight of 420. The hydroxyl value was 378.3mgKOH/g.
Synthesis example 4 Synthesis of polyester polyol (A-4)
To a polyester reaction vessel equipped with a stirrer, a nitrogen inlet pipe, a schner pipe, and a condenser, 35.17 parts of ethylene glycol, 15.40 parts of glycerin, 84.17 parts of phthalic anhydride, and 0.013 parts of titanium tetraisopropoxide were added, and the mixture was heated slowly so that the upper temperature of the rectifying pipe was not higher than 100 ℃, and the internal temperature was kept at 220 ℃. The esterification reaction was terminated at an acid value of 1mgKOH/g or less to obtain a polyester polyol (A-4) having a number average molecular weight of 1050. The hydroxyl value was 190.0mgKOH/g.
Synthesis example 5 Synthesis of polyester polyol (A-5)
56.53 Parts of ethylene glycol, 79.48 parts of phthalic anhydride and 0.007 parts of titanium tetraisopropoxide were added to a polyester reaction vessel equipped with a stirrer, a nitrogen inlet pipe, a schner pipe and a condenser, and the mixture was heated slowly so that the upper temperature of the rectifying pipe was not higher than 100℃and the internal temperature was kept at 220 ℃. After the esterification reaction was completed at an acid value of 1mgKOH/g or less, 0.01 part of phosphoric acid was added to obtain a polyester polyol (A-5) having a number average molecular weight of 400. The hydroxyl value was 280.0mgKOH/g.
Synthesis example 6 Synthesis of polyester polyol (A-6)
To a polyester reaction vessel equipped with a stirrer, a nitrogen inlet pipe, a schner pipe, and a condenser, 51.06 parts of ethylene glycol and 63.30 parts of phthalic anhydride were added, and the mixture was heated slowly so that the upper temperature of the rectifying pipe was not higher than 100℃and the internal temperature was kept at 220 ℃. After the esterification reaction was completed at an acid value of 1mgKOH/g or less, 0.01 part of phosphoric acid was added to obtain a polyester polyol (A-6) having a number average molecular weight of 340. The hydroxyl value was 331.0mgKOH/g.
Synthesis example 7 Synthesis of polyester polyol (A-7)
To a polyester reaction vessel equipped with a stirrer, a nitrogen inlet pipe, a schner pipe, and a condenser, 61.45 parts of ethylene glycol and 66.66 parts of phthalic anhydride were added, and the mixture was heated slowly so that the upper temperature of the rectifying pipe was not higher than 100℃and the internal temperature was kept at 220 ℃. After the esterification reaction was completed at an acid value of 1mgKOH/g or less, 0.01 part of phosphoric acid was added to obtain a polyester polyol (A-7) having a number average molecular weight of 256. The hydroxyl value was 438.0mgKOH/g.
Synthesis example 8 Synthesis of polyester polyol (A-8)
17.58 Parts of ethylene glycol, 71.84 parts of 1,3, 5-tris (2-hydroxyethyl) isocyanurate and 32.47 parts of succinic acid were added to a polyester reaction vessel equipped with a stirrer, a nitrogen inlet pipe, a Snyder pipe and a condenser, and the mixture was heated slowly so that the upper temperature of the rectifying pipe was not higher than 100℃and the internal temperature was kept at 220 ℃. After the esterification reaction was completed at an acid value of 1mgKOH/g or less, 0.01 part of phosphoric acid was added to obtain a polyester polyol (A-8) having a number average molecular weight of 420. The hydroxyl value was 410.3mgKOH/g.
< Synthesis of isocyanate Compound (B) >
Synthesis example 9 Synthesis of isocyanate Compound (B-1)
136.00 Parts of xylylene diisocyanate was added to a reaction vessel equipped with a stirrer, a nitrogen inlet pipe, a schider pipe, a cooling condenser and a dropping funnel, and stirred while being heated to 70 ℃, 116.00 parts of polyester polyol (a-5) was dropped using the dropping funnel for 2 hours, and further stirred for 4 hours to obtain an isocyanate compound (B-1). The NCO% measured in accordance with JIS-K1603 was 14.1%.
Synthesis example 10 Synthesis of isocyanate Compound (B-2)
136.00 Parts of xylylene diisocyanate was added to a reaction vessel equipped with a stirrer, a nitrogen inlet pipe, a Schneider pipe, a cooling condenser and a dropping funnel, and the mixture was stirred while being heated to 70℃to drop 99.50 parts of polyester polyol (A-5) using the dropping funnel for 2 hours and further stirred for 4 hours to obtain an isocyanate compound (B-2). The NCO% measured in accordance with JIS-K1603 was 16.0%.
Synthesis example 11 Synthesis of isocyanate Compound (B-3)
To a reaction vessel equipped with a stirrer, a nitrogen inlet tube, a Snyder tube, a cooling condenser and a dropping funnel, 125.00 parts of xylylene diisocyanate was added and stirred while heating to 70℃and 82.00 parts of polyester polyol (A-6) was dropped by using the dropping funnel for 2 hours and further stirred for 4 hours to obtain an isocyanate compound (B-3). The NCO% measured in accordance with JIS-K1603 was 16.6%.
Synthesis example 12 Synthesis of isocyanate Compound (B-4)
To a reaction vessel equipped with a stirrer, a nitrogen inlet tube, a Snyder tube, a cooling condenser and a dropping funnel, 136.47 parts of xylylene diisocyanate was added and stirred while heating to 70℃and 85.69 parts of polyester polyol (A-2) was dropped using the dropping funnel for 2 hours and stirred for further 4 hours to obtain an isocyanate compound (B-4). The NCO% measured in accordance with JIS-K1603 was 16.6%.
Synthesis example 13 Synthesis of isocyanate Compound (B-5)
To a reaction vessel equipped with a stirrer, a nitrogen inlet tube, a Snyder tube, a cooling condenser and a dropping funnel, 135.00 parts of xylylene diisocyanate was added and stirred while heating to 70℃and 75.00 parts of polyester polyol (A-7) was dropped by using the dropping funnel for 2 hours and further stirred for 4 hours to obtain an isocyanate compound (B-5). The NCO% measured in accordance with JIS-K1603 was 16.7%.
Synthesis example 14 Synthesis of isocyanate Compound (B-6)
136.00 Parts of xylylene diisocyanate was added to a reaction vessel equipped with a stirrer, a nitrogen inlet pipe, a schider pipe, a cooling condenser and a dropping funnel, and stirred while being heated to 70 ℃, 96.00 parts of polyester polyol (a-2) was dropped using the dropping funnel for 2 hours, and further stirred for 4 hours to obtain an isocyanate compound (B-6). The NCO% measured in accordance with JIS-K1603 was 14.5%.
Synthesis example 15 Synthesis of isocyanate Compound (B-7)
To a reaction vessel equipped with a stirrer, a nitrogen inlet tube, a Snyder tube, a cooling condenser and a dropping funnel, 126.00 parts of xylylene diisocyanate was added and stirred while heating to 70℃and 75.00 parts of polyester polyol (A-8) was dropped by using the dropping funnel for 2 hours and stirred for 4 hours to obtain an isocyanate compound (B-7). The NCO% measured in accordance with JIS-K1603 was 15.7%.
< Preparation of adhesive >
Example 1
Polyester polyol (A-1): 30.8 parts of an isocyanate compound (B-1): 84.0 parts of isosorbide as drying aid (D): 7.7 parts of the adhesive of example 1 was prepared by adjusting the solid content to 53% with ethyl acetate.
Examples 2 to 22
The adhesives of examples 2 to 22 were prepared in the same manner as in example 1, except that the polyester polyol (a), isocyanate compound (B), drying aid (D) and their compounding were changed to those shown in tables 1 to 4.
(Comparative examples 1) to (comparative example 4)
Adhesives of comparative examples 1 to 4 were prepared in the same manner as in example 1, except that the polyester polyol (a), isocyanate compound (B) and their compounding used were changed to those shown in table 5.
In the table, XDI is xylylene diisocyanate, and XDI-TMP adduct is trimethylolpropane adduct of xylylene diisocyanate.
< Production of laminate >
Example 1
As a first substrate, a substrate obtained by coating Finart R794 white G3 on an OPP film (manufactured by eastern spinning corporation, PYlen P, 2161) having a film thickness of 30 μm was prepared, and as a second substrate, a CPP film (manufactured by eastern spinning corporation, PYlen P, 1128) having a film thickness of 30 μm was prepared. The adhesive of example 1 was applied to the print surface of the first substrate so that the solid content was 3.0g/m 2, using a DL-600DX dry laminator (manufactured by Orient company) in which the transport speed of the first substrate and the second substrate was set to 100 m/min, and the temperature of the drying oven was set to 60 ℃ and 70 ℃ and 80 ℃ from the upstream side in the transport direction of the first substrate, respectively, and the adhesive was bonded to the second substrate. Curing was performed at 40℃for 3 days to obtain a laminate of example 1.
(Examples 2) to (22) and (comparative examples 1) to (4)
Laminates of examples 2 to 22 and comparative examples 1 to 4 were obtained in the same manner as in example 1, except that the first substrate, the second substrate, the adhesive and the conveyance speed of the substrate used were changed to those described in tables 1 to 5. The adhesive was applied to the right side of the first base material shown in the table, and the adhesive was bonded to the left side of the second base material. Therefore, for example, in example 6, an adhesive was applied to the printing layer side of the first base material and bonded to the aluminum vapor deposition layer of the second base material. The print layers of the first substrates used in examples 8, 11 and 12 were provided in the same manner as in example 1.
The substrates used in the examples and comparative examples are shown below.
OPP: manufactured by Toyo-yo corporation, PYlen P2161, and a film thickness of 30 μm
CPP (30): manufactured by Toyo-yo corporation, PYlen P, 1128 and a film thickness of 30 μm
CPP (70): toray film processing Co Ltd, ZK-207, film thickness 70 μm
VMCPP (25): toray film processing Co., ltd., 2203, film thickness 25 μm
VMCPP: manufactured by Toray film processing Co., ltd., 2703 and film thickness of 30 μm
PET: manufactured by Toyo-yo corporation, E5100, film thickness of 12 μm
PET-AlOx: toray film processing Co., ltd., barrilox 1011HG, film thickness 12 μm
PET-SiOx: mitsubishi chemical corporation, TECHBARRIER TX, film thickness 12 μm
Ny: UNITIKA, EMBLEM ON, film thickness 15 μm
LLDPE: sanjing Chemie Tohcello Co., ltd., T.U.X-HC, film thickness 60 μm
< Evaluation >
(Residual solvent amount)
The laminate of examples and comparative examples was placed in a 500cc flask and heated at 80℃for 30 minutes, and then the gas in the flask was measured by gas chromatography, and the results were converted to the amount of solvent (mg/m 2) per 1m 2 of the laminate, and the results were summarized in the table.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
As is clear from tables 1 to 5, the adhesive of the present invention can suppress the residue of the organic solvent in the cured coating film of the adhesive.

Claims (8)

1. A two-part curable adhesive comprising a polyester polyol A, an isocyanate compound B, an organic solvent C and a drying aid D.
2. The two-part curable adhesive according to claim 1, wherein,
The amount of the drying aid D is 0.5 to 50 mass% inclusive of the solid content of the adhesive.
3. The two-part curable adhesive according to claim 1 or 2, wherein,
The drying aid D is selected from isosorbide, isomannide and 1,4: at least one of 3, 6-dianhydro-L-iditol and triacetin.
4. The two-part curable adhesive according to any one of claims 1 to 3, wherein,
The drying aid D is isosorbide.
5. The two-part curable adhesive according to any one of claims 1 to 4, wherein,
The polyester polyol comprises at least one of a polyester polyol A2 obtained by polycondensing a polyhydric carboxylic acid comprising an ortho-oriented aromatic polyhydric carboxylic acid with a polyhydric alcohol, a polyester polyol A3 having an isocyanuric ring, and a polyester polyol A4 having a polymerizable carbon-carbon double bond.
6.A method for producing a laminate having a first substrate, a second substrate, and an adhesive layer for bonding the first substrate to the second substrate,
The manufacturing method comprises the following steps:
a step of providing a coating film of a two-component curable adhesive comprising a polyester polyol A, an isocyanate compound B, an organic solvent C and a drying aid D on the first substrate;
A step of conveying the first substrate to a drying device and heating the first substrate to volatilize the organic solvent C from the coating film of the adhesive;
bonding the first base material to the second base material via the coating film of the adhesive; and
And curing the coating film of the adhesive to form the adhesive layer.
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 adhesive according to any one of claims 1 to 5.
8. A packaging material comprising the laminate of claim 7.
CN202280069742.2A 2021-11-11 2022-10-27 Adhesive, laminate, and packaging material Pending CN118103472A (en)

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