CN109462992B - Urethane adhesive, cured product and laminated film thereof, polyol for adhesive, and polyisocyanate composition - Google Patents
Urethane adhesive, cured product and laminated film thereof, polyol for adhesive, and polyisocyanate composition Download PDFInfo
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- CN109462992B CN109462992B CN201780039001.9A CN201780039001A CN109462992B CN 109462992 B CN109462992 B CN 109462992B CN 201780039001 A CN201780039001 A CN 201780039001A CN 109462992 B CN109462992 B CN 109462992B
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- 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
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- 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
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
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- 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
- C09J135/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J135/06—Copolymers with vinyl aromatic monomers
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- 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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- 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 Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A urethane adhesive comprising a polyol (A) selected from the group consisting of polyester polyol, polyester polyether polyol, polyester polyurethane polyol, polyether polyurethane polyol and polyester polyether polyurethane polyol, a polyisocyanate (B) and a polyester-polyether polyurethane polyol having an SP value of 20 to 32 (J/cm)3)1/2And a carboxyl group-containing compound (C) having an acid value of 250 to 1000mgKOH/g as an essential component, wherein the carboxyl group-containing compound (C) is contained in a proportion of 0.01 to 1.5 parts by mass relative to 100 parts by mass of the polyol (A).
Description
Technical Field
The present invention relates to a urethane adhesive, a polyisocyanate mixture and a polyol mixture used for the same, and a laminated film obtained by laminating various films using the adhesive. More specifically, the present invention relates to a laminating adhesive used for producing a composite film mainly used for packaging materials such as foods, medicines, detergents, and the like by laminating various plastic films, metal vapor-deposited films, aluminum foils, and the like.
Background
Multilayer films obtained by so-called dry lamination in which an adhesive is applied to the surface of a film base, and then the adhesive is evaporated and dried to remove the solvent, and the film is laminated while heating and pressure-bonding other materials are widely used, because any combination of films can be selected according to the desired characteristics of each application.
The adhesive for dry lamination is mainly a two-component polyurethane adhesive mainly containing a polyol component having a hydroxyl group at the polymer terminal as a main component and a polyisocyanate as a curing agent. Here, as the polyol component, a polyester polyol or a polyester polyurethane polyol is used, and as the polyisocyanate, various monomeric polyisocyanates such as Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) and the like are used, from the viewpoint that the curing agent itself functions as a reactive diluent.
However, when a packaging laminate film is produced using a urethane adhesive containing the above polyester polyol or polyester polyurethane polyol as a main component, the adhesive layer of the multilayer film is easily damaged by etching with an acid component or an alkaline component contained in food or the like as a content.
In particular, in recent years, there have been increasing food packages (snacks, frozen foods, etc.) using aluminum vapor-deposited films, and when packaging acidic components such as vinegar and free fatty acids or alkaline foods contained in foods as contents, problems such as disappearance of aluminum vapor-deposited layers, disappearance of printed patterns, visibility of contents, and the like occur during display in storefronts after boiling sterilization treatment have been particularly prominent.
Therefore, for example, the following patent document 1 discloses the following technique: as an adhesive for laminating an aluminum foil and an unstretched polypropylene film in a multilayer film for food packaging, a urethane adhesive comprising a polyol obtained by modifying a polymer polyol with styrene-maleic anhydride and a polyisocyanate is used, whereby the compatibility between the polyol component and the polyisocyanate component is improved and the disappearance of an adhesive layer due to edible vinegar and free fatty acid derived from the contents is prevented.
However, in the adhesive described in patent document 1, since the amount of styrene-maleic anhydride used is large and about 6 parts by mass per 100 parts by mass of the polymer polyol, the viscosity of the adhesive itself increases, air is entrained during lamination processing, and the film appearance is lowered, and the adhesive layer becomes hard and brittle, so that the long-term adhesive strength cannot be obtained, and the disappearance of the aluminum deposition layer cannot be avoided during long-term use.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 3206946
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide an adhesive for laminating a resin film onto a laminated film, particularly a metal surface such as an aluminum foil or an aluminum deposited film, which has excellent processability and thus can provide a laminated film having good appearance and excellent adhesive strength over a long period of time, and to provide a main agent or a curing agent usable for the adhesive, and a multilayer film having excellent long-term stability and excellent appearance obtained by laminating the adhesive, which can suppress the disappearance of a metal deposited layer over a long period of time when the metal deposited film is used as a base film.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present inventors have found that an adhesive of a polyol/polyisocyanate, which is excellent in long-term stability of a multilayer film and also excellent in appearance of the multilayer film by exhibiting good processability, can be obtained by using a carboxyl group-containing compound having a specific SP value as an additive component in an amount of 0.01 to 1.5 parts by mass relative to 100 parts by mass of the polyol.
That is, the present invention provides a urethane adhesive comprising: selected from the group consisting of polyester polyols (a1), polyester urethane polyols (a2) and polyethersThe polyol (A), polyisocyanate (B) and SP value in the group consisting of urethane polyol (a3) are 20-32 (J/cm)3)1/2And a carboxyl group-containing compound (C) having an acid value of 250 to 1000mgKOH/g, wherein the carboxyl group-containing compound (C) is contained in an amount of 0.01 to 1.5 parts by mass per 100 parts by mass of the polyol (A).
The present invention also provides a polyol composition for a urethane adhesive, which contains: a polyol (A) selected from the group consisting of polyester polyol (a1), polyester urethane polyol (a2) and polyether urethane polyol (a3), and having an SP value of 20 to 32 (J/cm)3)1/2And a carboxyl group-containing compound (C) having an acid value of 250 to 1000mgKOH/g, wherein the carboxyl group-containing compound (C) is contained in an amount of 0.01 to 1.5 parts by mass per 100 parts by mass of the polyol (A).
The invention also provides a polyisocyanate composition for a urethane adhesive, which contains a polyisocyanate (B) and has an SP value of 20 to 32 (J/cm)3)1/2And a carboxyl group-containing compound (C) having an acid value of 250 to 1000 mgKOH/g.
The present invention also provides a cured product obtained by curing the urethane adhesive.
The present invention also provides a laminate film obtained by applying the urethane adhesive to a first base film, laminating a second base film on the applied surface, and curing the adhesive layer.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide an adhesive for laminating a resin film, particularly a metal surface such as an aluminum foil or an aluminum deposited film, which has excellent processability, has good appearance of a laminated film, and has excellent long-term adhesive strength, a main agent or a curing agent thereof, and a multilayer film obtained by laminating the adhesive and having excellent long-term stability and appearance.
Detailed Description
As described above, the urethane adhesive of the present invention is characterized in that the adhesive is prepared from a polyester polyol (a1), a polyester urethane polyol (a2) and a polyether amino groupA polyol (A), a polyisocyanate (B) and an SP value of 20 to 32 (J/cm) in the group consisting of a formate polyol (a3)3)1/2And a carboxyl group-containing compound (C) having an acid value of 250 to 1000mgKOH/g as an essential component, wherein the carboxyl group-containing compound (C) is contained in a proportion of 0.01 to 1.5 parts by mass relative to 100 parts by mass of the polyol (A). The urethane adhesive is a two-component adhesive of polyol (a)/polyisocyanate (B), and the carboxyl group-containing compound (C) may be used in the form of a polyol composition blended with the polyol (a) or in the form of a polyisocyanate composition blended with the polyisocyanate (B). Alternatively, when the adhesive is used, the polyol (a) and the polyisocyanate (B) may be mixed at the same time.
In the present invention, it is extremely important to use the carboxyl group-containing compound (C) in a proportion of 0.01 to 1.5 parts by mass relative to 100 parts by mass of the polyol (a). When the amount of the carboxyl group-containing compound (C) is less than 0.01 part by mass, the effect of preventing delamination by the addition of the carboxyl group-containing compound (C) cannot be exhibited, and when it exceeds 1.5 parts by mass, the adhesive layer itself becomes hard and brittle, and long-term adhesive strength cannot be obtained.
As previously mentioned, the polyol (a) used herein is selected from the group consisting of a polyester polyol (a1), a polyester urethane polyol (a2) and a polyether urethane polyol (a 3). The urethane adhesive containing these polyol components exhibits excellent adhesive performance and workability, while the adhesive layer is easily broken when the contents contain an acidic substance or a basic substance, and the disappearance of the adhesive layer due to the acidic substance or the basic substance can be effectively prevented by using the carboxyl group-containing compound (C) as an additive.
Specific examples of the polyester polyol (a1) constituting the polyol (a) include: a polyester polyol (a1-1) obtained by reacting an aliphatic polyhydric alcohol with an aliphatic polycarboxylic acid, a polyester polyol (a1-2) obtained by reacting an aliphatic polyhydric alcohol with an aromatic polycarboxylic acid, and a polyester polyol (a1-3) which is a reactant of a polyester obtained by a ring-opening polymerization reaction of an aliphatic cyclic ester compound and an aliphatic polyhydric alcohol.
Examples of the aliphatic polyol which is a raw material of the polyester polyols (a1-1) to (a1-3) include: aliphatic diols such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutylene glycol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, and triethylene glycol; trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane and pentaerythritol; a dihydric alcohol; and aliphatic polyether polyols as ring-opening polymers of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexene oxide.
On the other hand, examples of the aliphatic polycarboxylic acid to be a raw material of the polyester polyol (a1-1) include: examples of the aromatic polycarboxylic acid which is a raw material of the polyester polyol (a1-2) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1, 3-cyclopentanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, and dimer acid: terephthalic acid, isophthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1, 2-bis (phenoxy) ethane-p, p' -dicarboxylic acid, and the like.
Examples of the aliphatic cyclic ester compound which is a raw material of the polyester polyol (a1-3) include propiolactone, butyrolactone, epsilon-caprolactone, zeta-valerolactone, β -methyl zeta-valerolactone, and the like.
The polyester polyol (a1) described in detail above preferably has a number average molecular weight (Mn) of 3000 to 5000 and a weight average molecular weight (Mw) of 8000 to 15000, from the viewpoints of high resistance to acidic and basic substances and excellent content resistance. The hydroxyl value is preferably in the range of 3 to 50mgKOH/g from the viewpoint of excellent wettability with the substrate.
In the present invention, the number average molecular weight (Mn) or the weight average molecular weight (Mw) is a value measured by Gel Permeation Chromatography (GPC) under the following conditions.
A measuring device: HLC-8220GPC manufactured by TOSOH CORPORATION
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by TOSOH CORPORATION
+ TSK-GEL SuperHZM-Mx 4 manufactured by TOSOH CORPORATION
A detector: RI (differential refractometer)
Data processing: TOSOH CORPORATION manufactures Multi-Station GPC-8020model II
The measurement conditions were as follows: column temperature 40 deg.C
Solvent tetrahydrofuran
Flow rate 0.35 ml/min
The standard is as follows: monodisperse polystyrene
Sample preparation: the resulting tetrahydrofuran solution (0.2 mass% in terms of resin solid content) was filtered through a microfilter (100. mu.l)
Next, the polyester polyurethane polyol (a2) is a polyol having a urethane bond in the molecular structure, which is obtained by modifying the polyester polyol (a1) with a polyisocyanate.
Examples of the polyisocyanate used herein include: polyisocyanates having an alicyclic structure in the molecular structure, such as isophorone diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), and 1,3- (isocyanatomethyl) cyclohexane; linear aliphatic polyisocyanates such as 1, 6-hexamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate; and aromatic polyisocyanates such as toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, and triphenylmethane triisocyanate.
In the present invention, the polyester polyurethane polyol (a2) is preferably a polyester polyurethane polyol (a2-1) having a side chain containing an alkyl chain of 6 or more carbon atoms derived from a dimer acid or a diol and having a branching point concentration of the side chain of 0.2mmol (hereinafter, mmol/g) or more per 1 g of the solid content of the adhesive composition, from the viewpoint of providing an adhesive having good initial adhesion and excellent heat resistance, water resistance, oil resistance, hot water resistance, and alkali resistance.
Here, the dimer acid is a product obtained by Diels-Alder (Diels-Alder) dimerization of long-chain unsaturated fatty acids such as oleic acid and linoleic acid, and various substances such as a substance obtained by hydrogenating unsaturated bonds to saturate the unsaturated bonds are included, and examples thereof include substances composed of 0 to 5% by weight of a monocarboxylic acid of C18, 70 to 98% by weight of a dimer acid of C36, and 0 to 30% by weight of a trimer acid of C54. The dimer acid is obtained by reducing the dimer acid described above.
When the concentration of the branch point of the side chain having a molecular weight of 70 or more is small, the change in the dynamic viscoelasticity ratio is small and desired physical properties cannot be obtained, and therefore the concentration of the branch point is preferably 0.2mmol/g or more based on the adhesive solid content.
The polyester urethane polyol (a2-1) described in detail above preferably has a number average molecular weight (Mn) of 8000 to 15000 and a weight average molecular weight (Mw) of 25000 to 35000, in view of adhesive strength and fluidity. Further, from the viewpoint of excellent wettability with the substrate, a hydroxyl value in the range of 2 to 15mgKOH/g is preferable.
The polyester polyurethane polyol (a2) is preferably used in combination with the aliphatic diol and the trifunctional or tetrafunctional aliphatic alcohol as the raw alcohol components, and in combination with the long-chain aliphatic dicarboxylic acid having from C9 to C12, such as azelaic acid, sebacic acid (C10) or dodecanedicarboxylic acid, and the aromatic dicarboxylic acid as the raw carboxylic acid components, in addition to the polyester polyurethane polyol (a2-1), and the polyester polyurethane polyol (a2-2) obtained by reacting the polyester obtained by the esterification reaction with the polyisocyanate having the alicyclic structure is preferable in view of having excellent adhesive strength and appropriate flexibility and thus being capable of being used in retort pouches (retortable pouches) having excellent retort resistance.
In view of the above-mentioned steaming resistance, the polyester urethane polyol (a2-2) described in detail above preferably has a number average molecular weight (Mn) of 7000 to 10000 and a weight average molecular weight (Mw) of 25000 to 40000. Further, from the viewpoint of excellent wettability with the substrate, a hydroxyl value in the range of 2 to 15mgKOH/g is preferable.
Next, as the polyether polyurethane polyol (a3), there can be mentioned a urethane bond-containing polyether polyol having a resin structure obtained by polymerizing a polyether polyol, which is: polyether polyols obtained by addition polymerization of glycols such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutylene glycol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, and triethylene glycol with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, phenylethylene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexene oxide in the presence of a polymerization initiator.
The polyether polyurethane polyol (a3) described in detail above preferably has a number average molecular weight (Mn) in the range of 4000 to 6000 and a weight average molecular weight (Mw) in the range of 14000 to 20000, since it has excellent fluidity and can cope with high-speed lamination. Further, a hydroxyl value in the range of 3 to 25mgKOH/g is preferable from the viewpoint of excellent wettability with the substrate.
The carboxyl group-containing compound (C) having an SP value of 13.00 to 15.00 and an acid value of 250 to 1000mgKOH/g is a component for exhibiting a laminate strength, particularly an excellent adhesive property to a metal vapor-deposited surface or a metal thin film.
Here, the SP value is a value (. delta.) calculated from the cohesive energy density and molar molecular volume of the chemical structure according to the following formula by means of Fedors' calculation
Here, the Fedors calculation method is a calculation method shown in the following document.
[ document ]
R.F.Fedors，Polym.Eng.Sci.，14〔2〕、145-154,1974
In the formula, Ecoh represents the cohesive energy density of each structural unit constituting the chemical structure. For example, -CH2-is 4940J/mole, -CH34710J/mol, -CO-17360J/mol, -COO-18000J/mol, -COOH-27630J/mol, - (CH-4,310J/mol, -CH<3430J/mole, -OH 29800J/mole, -O-3350J/mole, etc.
On the other hand, V is the molar molecular volume of each structural unit constituting the chemical structure, e.g., -CH2-16.1 cm3Mole and-CH3Is 33.5cm3Mol and-CO-10.8 cm3Mol and-COO-18.0 cm3Mol, -COOH was 28.5cm313.5 cm/mol, ═ CH-3Mole and-CH<Is-1.0 cm3Mol and-OH 10.0cm3Mol and-O-is 3.8cm3And the like.
The SP value of the carboxyl-containing compound (C) used in the invention is 20-32 (J/cm)3)1/2Therefore, the resin composition has excellent compatibility with the polyol (a) or the polyisocyanate (B), and can effectively eliminate the influence of acidic substances and basic substances contained in the resin composition.
In the present invention, since the acid value of the carboxyl group-containing compound (C) is in the range of 250 to 1000mgKOH/g, the adhesion to a substrate is excellent, and particularly the adhesion to a metal foil substrate or a metal vapor deposition surface is excellent.
Here, specific examples of the carboxyl group-containing compound (C) include: a copolymer of aromatic vinyl and maleic anhydride (c1), a hydroxyl group-containing aliphatic carboxylic acid (c2), and a tetrahydrophthalic anhydride backbone (c 3).
The aromatic ethylene/maleic anhydride copolymer (c1) is preferably such that the aromatic ethylene/maleic anhydride copolymer (c1) has a monomer composition ratio ([ aromatic ethylene/maleic anhydride ] molar ratio) in the range of 1.5/1 to 5/1, from the viewpoint of excellent compatibility with the polyol (a) and particularly excellent lamination strength even after long-term storage of the adhesive. In particular, the weight average molecular weight is preferably in the range of 1000 to 4000 from the viewpoint of compatibility with the polyol (A), and the acid value is preferably in the range of 0.1 to 20mgKOH/g from the viewpoint of adhesive strength and PAA elution prevention.
Specific examples of the aromatic vinyl constituting the aromatic vinyl/maleic anhydride copolymer (c1) include styrene, α -methylstyrene and divinylbenzene, and among them, styrene is preferable from the viewpoint of excellent compatibility with the polyisocyanate (B) described later.
The SP value of the aromatic ethylene/maleic anhydride copolymer (c1) may be calculated from the presence ratio of aromatic ethylene to maleic anhydride by calculating the SP value (δ) of each of the structural unit(s) derived from aromatic ethylene and the structural unit (m) derived from maleic anhydride. For example, the molar ratio of aromatic ethylene to maleic anhydride is 1: 1, the sum of the SP value of the structural unit(s) derived from aromatic ethylene and the SP value of the structural unit (m) derived from maleic anhydride can be simply calculated, and the molar ratio of aromatic ethylene to maleic anhydride is 2: in the case of the copolymer of 1, the SP value of the structural unit(s) may be multiplied by 2 and added to the SP value of the structural unit (m).
Specifically 1: 1 (molar ratio) of the reactants, the SP value was 31.4 (J/cm)3)1/2。
Next, examples of the hydroxyl group-containing aliphatic carboxylic acid (C2) used for the carboxyl group-containing compound (C) include: 2, 2-bis (hydroxymethyl) propionic acid [ SP value 28.7 (J/cm)3)1/2Acid value 414-418mgKOH/g]2, 2-bis (hydroxymethyl) butanoic acid SP value 27.4 (J/cm)3)1/2Acid value 374-378mgKOH/g]And the like.
Next, examples of the compound (C3) having a tetrahydrophthalic anhydride skeleton used as the carboxyl-group-containing compound (C) include: tetrahydrofuran [ SP value 27.7 (J/cm)3)1/2And an acid value of 675mgKOH/g]The following structural formula1, shown in,
3a,4,5,7 a-tetrahydro-7-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -1, 3-iso-benzofurandione [ SP value 29.1 (J/cm)3)1/2Acid value 849mgKOH/g]。
Here, the aromatic vinyl/maleic anhydride copolymer (c1) is preferably used as an ethyl acetate solution when blended into the polyester polyol (a1), the polyester urethane polyol (a2), or the polyether urethane polyol (a3) as a main agent in the dry lamination adhesive, because it exhibits excellent solubility in ethyl acetate, which is a solvent commonly used in dry lamination adhesives.
Further, the hydroxyl group-containing aliphatic carboxylic acid (c2) is preferable in that it exhibits excellent solubility in the polyether urethane polyol (a3), and is used as a main component polyol component for dry lamination which is blended with the polyether urethane polyol (a3) and dissolved in ethyl acetate, whereby an adhesive suitable for high-speed lamination can be produced.
The compound (c3) having a tetrahydrophthalic anhydride skeleton is preferably used as a dry laminating adhesive or a solvent-free adhesive because of its good compatibility with the polyol (a) and the polyisocyanate (B), and is preferably used, for example, as a curing agent component of a dry laminating adhesive by being mixed with the polyisocyanate (B), so that the present invention can be applied to various product variations.
Next, examples of the polyisocyanate (B) used in the present invention include: polyisocyanates having an aromatic structure in the molecular structure, such as toluene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, triphenylmethane triisocyanate, and xylylene diisocyanate; polyisocyanates having an alicyclic structure in the molecular structure, such as isophorone diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), and 1,3- (isocyanatomethyl) cyclohexane; linear aliphatic polyisocyanates such as 1, 6-hexamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate; adduct-type polyisocyanate obtained by adding 3 moles of diisocyanate compound to 1 mole of trimethylolpropane; a biuret type polyisocyanate obtained by reacting 3 moles of diisocyanate with 1 mole of water, or an isocyanurate type polyisocyanate obtained by trimerizing a diisocyanate compound; and a polyurethane polyisocyanate compound (b3) obtained by reacting a polyisocyanate with a polyester polyol, a polyether polyol, or further a low-molecular polyol.
Here, the polyester polyol used as a raw material of the polyurethane polyisocyanate compound (b3) includes the polyester polyol (a1), and the polyether polyol includes: aliphatic diols such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutylene glycol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol and triethylene glycol.
Among these polyisocyanates (B), particularly, as a solvent-type adhesive, from the viewpoint of excellent curability and good adhesive strength, preferred are: a urethane product of a polyisocyanate having an alicyclic structure in its molecular structure; adduct type polyisocyanate having a structure in which 3 moles of xylylene diisocyanate is added to 1 mole of trimethylolpropane: an adduct-type polyisocyanate obtained by adding 3 moles of toluene diisocyanate to 1 mole of trimethylolpropane; polypropylene glycol modifications of methylene diisocyanate.
As described above, the urethane adhesive of the present invention composed of the components described in detail above can be used as a solvent-based adhesive or a solvent-free adhesive.
The solvent used for the solvent-based adhesive may be a solvent used as a reaction medium in the production of the polyol (a) and the polyisocyanate (B), or a solvent used as a diluent in the coating. Examples of the solvent that can be used here include: esters such as ethyl acetate, butyl acetate, cellosolve acetate, and the like; 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 dichloromethane and dichloroethane; dimethylsulfoxide, dimethylsulfonamide, and the like. Among these, ethyl acetate or methyl ethyl ketone is preferably used in view of easy recovery/reuse.
As described above, the urethane adhesive of the present invention is a two-component curing type urethane adhesive, and can be used in the following form: the polyol composition (X) obtained by previously blending the carboxyl group-containing compound (C) with the polyol (a), or the polyisocyanate composition (Y) obtained by blending the carboxyl group-containing compound (C) with the polyisocyanate (B).
That is, in the case of a solvent-type two-component urethane adhesive, the polyol composition (X) may be used as a two-component main agent and the polyisocyanate (B) may be used as a curing agent; alternatively, the polyol (a) may be used as a main agent and the polyisocyanate composition (Y) may be used as a curing agent.
On the other hand, in the case of a solvent-free two-component urethane adhesive, the polyisocyanate composition (Y) may be used as a main agent and the polyol (a) may be used as a curing agent; alternatively, the polyisocyanate (B) may be used as a main agent and the polyol composition (X) may be used as a curing agent.
Here, as described above, in the case of the polyol composition (X) which is a solvent-based adhesive containing the polyol (a) and the carboxyl group-containing compound (C) as essential components, an organic solvent may be used.
On the other hand, in the case where the polyisocyanate composition (Y) is a solvent-type adhesive containing the polyisocyanate (B) and the carboxyl group-containing compound (C) as essential components, an organic solvent may be used.
As described above, the urethane adhesive of the present invention can be used as a solvent-type adhesive or a solvent-free adhesive, and is preferably used as a solvent-type adhesive in terms of excellent long-term storage stability and good workability. Here, in order to prepare a solvent-based two-component type urethane adhesive, it is preferable that the solid content of the main agent and the solid content of the curing agent are adjusted to 50 to 80 mass% by the organic solvent, respectively, and the organic solvent is added in a state of being mixed with the two components at the time of use, if necessary, so that the lamination workability is excellent when the solid content is finally made to be in the range of 20 to 40 mass%.
In the present invention, when the carboxyl group-containing compound (C) is used as the polyol composition (X) or as the polyisocyanate composition (Y), the carboxyl group-containing compound (C) is used in a proportion of 0.01 to 1.5 parts by mass relative to 100 parts by mass of the polyol (a), whereby the processability in the lamination process is improved, the appearance of the obtained laminated film is improved, and the etching of acid or alkali derived from the content can be prevented for a long period of time.
The urethane adhesive of the present invention is preferable in that the equivalent ratio [ isocyanate group/hydroxyl group ] of the isocyanate group in the polyisocyanate (B) to the hydroxyl group in the polyol (a) is in the range of 1.5 to 2.5, the strength/flexibility of the adhesive layer is in an appropriate range, and the initial adhesive strength, the long-term adhesive strength, and further the laminate appearance are good.
Therefore, the ratio of the polyol composition (X) to the polyisocyanate (B) or the ratio of the polyol (a) to the polyisocyanate composition (Y) is desirably in the range of 1.5 to 2.5 in equivalent ratio [ isocyanate group/hydroxyl group ].
By further adding an aliphatic cyclic amide compound to the urethane adhesive of the present invention, elution of harmful low-molecular-weight chemical substances such as aromatic amines into the contents in the laminated packaging body can be effectively suppressed. The above-mentioned aliphatic cyclic amide compound may be used by being compounded in any one of the polyol composition (X) and the polyisocyanate (B), or in any one of the polyol (a) and the polyisocyanate composition (Y), or by being compounded at the time of coating as the 3 rd component.
The aliphatic cyclic amide compound used here includes, for example, delta-valerolactam, epsilon-caprolactam, omega-enantholactam, η -caprylolactone, β -propiolactone, etc., among which epsilon-caprolactam is preferable from the viewpoint of excellent effect of reducing the elution amount of low-molecular chemical substances, and the aliphatic cyclic amide compound is preferably mixed in an amount of 0.1 to 5 parts by mass based on 100 parts by mass of the polyol composition (X).
The urethane adhesive of the present invention may be used in combination with a pigment as needed. The pigment that can be used in this case is not particularly limited, and examples thereof include: the paint raw materials are organic pigments such as extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, pearl pigments, inorganic pigments, and plastic pigments described in 1970 edition (edited by japan paint industries). Specific examples of these colorants include various ones, and examples of the organic pigment include: benzidine yellow, fast yellow, pigment red 4R, and various insoluble azo pigments; soluble azo pigments such as pigment red C, CARMINE 6B and purplish red 10; various (copper) phthalocyanine-based pigments such as phthalocyanine blue and phthalocyanine green; various chlorine-containing dyeing lakes such as rhodamine lake and methyl violet lake; various mordant dye-based pigments such as quinoline lake and fast blue; various dye-building pigments such as anthraquinone pigments, thioindigo pigments, and perinone pigments; various quinacridone pigments such as bright noble red B; various dioxazine pigments such as dioxazine violet; various condensed azo pigments such as leaf pigments; nigrosine and the like.
Examples of the inorganic pigment include: various chromates such as chrome yellow, zinc chromate, molybdenum orange, etc.; various ferrocyanide compounds such as prussian blue; various metal oxides such as titanium oxide, zinc white, velcade yellow, iron oxide, indian red, chromium oxide green, and zirconium oxide; various sulfides or selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various 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, brass powder, and the like; flake pigments of these metals, mica flake pigments; metal pigments such as mica flake pigments coated with metal oxides and mica-like iron oxide pigments, and pearlescent pigments; graphite, carbon black, and the like.
Examples of the extender pigment include: precipitated barium sulfate, chalk powder, precipitated calcium carbonate, calcium bicarbonate, Mediterranite, alumina white, Silica, hydrated Silica fine powder (white carbon), anhydrous Silica ultrafine powder (aerosil), Silica sand (Silica sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, and the like.
Further, examples of the plastic pigment include: "GRANDOLL PP-1000" and "PP-2000S" available from DIC corporation.
The pigment used in the present invention is more preferably an inorganic oxide such as titanium oxide or zinc white as a white pigment or carbon black as a black pigment, from the viewpoint of excellent durability, weather resistance and appearance.
The mass ratio of the pigment used in the present invention is more preferably 1 to 400 parts by mass, particularly 10 to 300 parts by mass, based on 100 parts by mass of the total of the polyisocyanate composition (X) and the polyol (Y), from the viewpoint of excellent adhesiveness, blocking resistance, and the like.
In addition, an adhesion promoter may be used as the urethane adhesive of the present invention. Examples of the adhesion promoter include: silane coupling agents, titanate coupling agents, aluminum coupling agents, and epoxy resins.
Examples of the silane coupling agent include aminosilanes such as γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethyldimethoxysilane and N-phenyl- γ -aminopropyltrimethoxysilane, epoxysilanes such as β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ -glycidoxypropyltrimethoxysilane and γ -glycidoxypropyltriethoxysilane, vinylsilanes such as vinyltris (β -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and γ -methacryloxypropyltrimethoxysilane, hexamethyldisilazane and γ -mercaptopropyltrimethoxysilane.
Examples of the titanate-based coupling agent include: titanium tetraisopropoxide, titanium tetra-n-butoxide, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctanediol titanate, titanium tetrastearoxy, and the like.
Examples of the aluminum-based coupling agent include aluminum acetyl alkoxy diisopropoxide.
Examples of the epoxy resin include various epoxy resins such as conventionally commercially available epi-bis type, novolak type, β -methyl epichlorohydrin type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, polycarboxylic acid ester type, amino glycidyl ester type, and resorcinol type.
The urethane adhesive of the present invention may contain other additives than those described above, if necessary. Examples of additives include: leveling agent; colloidal silica, alumina sol, and other inorganic fine particles; polymethyl methacrylate-based organic fine particles; defoaming agents; an anti-sagging agent; a wetting dispersant; a viscosity modifier; an ultraviolet absorber; a metal deactivator; a peroxide decomposer; a flame retardant; an enhancer; a plasticizer; a lubricant; a rust inhibitor; a fluorescent whitening agent; an inorganic heat ray absorber; a fire retardant; an antistatic agent; dehydrating agents and the like.
These pigments, adhesion promoters, and additives may be mixed in the ingredients of either the polyol composition and the polyisocyanate, or may be used as the 3 rd component to be compounded at the time of coating.
The urethane adhesive of the present invention described in detail above is cured under ordinary polyol/isocyanate curing conditions to obtain a cured product of the present invention.
Further, the laminated film of the present invention is obtained by: the urethane adhesive of the present invention described in detail above is applied to a first plastic film, and then a second plastic film is laminated on the applied surface, and the adhesive layer is cured.
Specifically, when the urethane adhesive of the present invention is used as a solvent-type adhesive, the following methods are exemplified: the urethane adhesive of the present invention is applied to a first plastic film by, for example, a roll coater, and then dried at 60 to 90 ℃, followed by bonding to other substrates. In the case of a general roll coater, the coating conditions are preferably about 500 to 2500 mPas in a state of being heated to about 25 to 120 ℃.
On the other hand, in the case of a solvent-free type, the following methods can be mentioned: the urethane adhesive of the present invention is applied to a first plastic film by, for example, coating with a roll coater, and then bonded to another base material without a drying step. The coating conditions are preferably about 500 to 2500 mPas in a state of being heated to about 25 to 120 ℃ in the case of a general roll coater.
The coating amount is about 1.0 to 4.0g/m in the case of solvent-based coating2Preferably, the amount of the solvent-free solvent is about 0.5 to 3.0g/m2It is suitable for left and right use. In the case of the solvent-free type, when the urethane adhesive of the present invention is used, the adhesive is cured at normal temperature or under heating for 6 to 24 hours after lamination, and practical properties are exhibited.
Examples of the first plastic film used herein include: base films such as PET (polyethylene terephthalate) films, nylon films, OPP (biaxially oriented polypropylene) films, aluminum vapor deposition films, aluminum foils, and the like, and other substrates include: sealing films such as CPP (non-stretched polypropylene) films and LLDPE (linear low density polyethylene) films.
As described above, in the present invention, the first plastic film is particularly preferably an aluminum foil or an aluminum vapor-deposited film in order to have excellent adhesion performance and durability/stability to a metal surface.
The laminated film thus obtained can be used industrially mainly as a packaging material filled with detergents and reagents. Specific applications include detergents and reagents, including: liquid detergents for washing, liquid detergents for kitchen, liquid detergents for bath, liquid soaps for bath, liquid shampoos, liquid conditioners, and the like.
The packaging material produced using the urethane adhesive of the present invention has excellent adhesiveness and content resistance, because the laminated structure is not peeled off even after a lapse of time after filling the packaging material with the contents such as a detergent and a reagent.
Examples
The contents and effects of the present invention will be described in further detail below with reference to examples. Further, the following are the raw material polyols used as raw materials in the respective examples and comparative examples. The number average molecular weight (Mn) shown in each example, comparative example, and synthetic example is a value measured by Gel Permeation Chromatography (GPC) under the following conditions.
A measuring device: HLC-8220GPC manufactured by TOSOH CORPORATION
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by TOSOH CORPORATION
+ TSK-GEL SuperHZM-Mx 4 manufactured by TOSOH CORPORATION
A detector: RI (differential refractometer)
Data processing: TOSOH CORPORATION manufactures Multi-Station GPC-8020model II
The measurement conditions were as follows: column temperature 40 deg.C
Solvent tetrahydrofuran
Flow rate 0.35 ml/min
The standard is as follows: monodisperse polystyrene
Sample preparation: the resulting tetrahydrofuran solution (0.2 mass% in terms of resin solid content) was filtered through a microfilter (100. mu.l)
Example 1 (production of polyol composition (x 1))
198 parts by mass of terephthalic acid, 162 parts by mass of isophthalic acid, 171 parts by mass of adipic acid, 127 parts by mass of ethylene glycol, 159 parts by mass of diethylene glycol, and 0.14 part by mass of dibutyltin dilaurate were charged into a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, a rectifying tube, a water separator, and the like, and the internal temperature was maintained at 250 ℃ while slowly heating so that the upper temperature of the rectifying tube did not exceed 100 ℃.
Xylene was refluxed at 240 ℃ by adding xylene when the acid value was 2.5mgKOH/g, and the reaction was continued until the acid value was 1.5mgKOH/g or less. The pressure was reduced to 1333Pa or less, the reaction was maintained for 1.5 hours, xylene was removed, and the esterification reaction was terminated to obtain a polyester polyol having a number average molecular weight (Mn) of about 4000.
To this, a styrene-maleic anhydride copolymer ("SMA 1000" manufactured by Cray Valley, styrene/maleic anhydride ═ 1/1 copolymer having a molecular weight of 5500SP value of 31.4 (J/cm) was added in a proportion of 0.5 parts by mass in terms of solid content to 100 parts by mass of the polyester polyol3)1/2) Further, the solid content was adjusted to a 75 mass% solution by dissolving and diluting the polyol in ethyl acetate to obtain a polyol composition (hereinafter, this will be abbreviated as "polyol composition (x 1)". ).
Example 2 (production of polyol composition (x 2))
The same polyester polyol was synthesized by the preparation method shown in example 1 using the same raw materials, in which 2, 2-bis (hydroxymethyl) propionic acid (DMPA) [ SP value 28.7 (J/cm) was added in a proportion of 0.5 parts by mass in terms of solid content relative to 100 parts by mass of the aforementioned polyester polyol3)1/2Acid value 414-418mgKOH/g]Further, the solid content was adjusted to a 75 mass% solution by dissolving and diluting the polyol in ethyl acetate to obtain a polyol composition (hereinafter, this will be abbreviated as "polyol composition (x 2)").
Example 3 (production of polyol composition (x 3))
The same polyester polyol was synthesized according to the preparation method shown in example 1 and using the same raw materials, whereuponIn which 2, 2-bis (hydroxymethyl) butanoic acid (DMBA) [ SP value 27.4 (J/cm) is added in a proportion of 0.5 parts by mass in terms of solid content to 100 parts by mass of the polyester polyol3)1/2Acid value 374-378mgKOH/g]Further, the solid content was adjusted to a 75 mass% solution by dissolving and diluting the polyol in ethyl acetate to obtain a polyol composition (hereinafter, this will be abbreviated as "polyol composition (x 3)").
Example 4 (production of polyol composition (x 4))
A flask equipped with a stirrer, a thermometer and a nitrogen inlet was charged with 170 parts by mass of toluene diisocyanate, 410 parts by mass of a polypropylene glycol having an average molecular weight of 700 (DIOL-700, a bifunctional polypropylene glycol manufactured by Mitsui chemical Co., Ltd.), and 70 parts by mass of a polypropylene glycol having an average molecular weight of 3000 (a bifunctional polypropylene glycol having an average molecular weight of 3000, manufactured by Mitsui chemical Co., Ltd.), and the mixture was heated to 95 ℃ and stirred for 1 hour, and then the temperature was lowered to 70 ℃ to add 25 parts by mass of dipropylene glycol and 2, 2-bis (hydroxymethyl) propionic acid (DMPA) [ SP value 28.7 (J/cm) to the mixture3)1/2Acid value 414-418mgKOH/g]7 parts by mass, dissolved until transparent.
Further, a mixture polyol composition of a polyester polyol having a number average molecular weight (Mn) of about 4600 and 2, 2-bis (hydroxymethyl) propionic acid (1 part by mass in terms of solid content relative to 100 parts by mass of the polyether urethane polyol) was obtained by reducing the temperature to 65 ℃ and adding 27 parts by mass of Diethanolamine (DEA) and 0.04 part by mass of dibutyltin dilaurate, and stirring for 1 hour (hereinafter, this will be abbreviated as "polyol composition (x 4)").
Synthesis example 1 (production of polyol (x5) (polyester urethane polyol))
123.5 parts by mass of terephthalic acid, 123.5 parts by mass of isophthalic acid, 139.5 parts by mass of adipic acid, 47 parts by mass of dimer acid, 62 parts by mass of ethylene glycol, 131 parts by mass of neopentyl glycol, 59 parts by mass of 1, 6-hexanediol, and 0.12 part by mass of dibutyltin dilaurate were put into a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a rectifying tube, a moisture separator, and the like, and the inside temperature was maintained at 240 ℃ while slowly heating so that the upper temperature of the rectifying tube did not exceed 100 ℃.
Xylene was refluxed at 230 ℃ by adding xylene to the mixture at an acid value of 2.5mgKOH/g using a moisture separator, and the reaction was continued until the acid value was 1.5mgKOH/g or less. The pressure was reduced to 1333Pa or less, xylene was removed by keeping for 1.5 hours, and the esterification reaction was terminated to obtain an intermediate polyester polyol having an acid value of 0.5 mgKOH/g. The solution was dissolved and diluted with ethyl acetate to prepare a solution having a solid content of 60% by mass. Further, 3 parts by mass of isophorone diisocyanate and 0.05 part by mass of dibutyltin dilaurate were added to 100 parts by mass of the obtained intermediate polyester polyol, and the mixture was heated to 80 ℃ to perform a urethanization reaction until substantially no free NCO groups were present, thereby obtaining a polyester urethane polyol having a hydroxyl value of 5 (hereinafter, this is abbreviated as "polyol (x 5)"). The polyester urethane polyol has a number average molecular weight (Mn) of about 11000.
Synthesis example 2 (production of polyol (x6) (polyester urethane polyol))
In a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, a rectifying tube, a moisture separator and the like, 827 parts by mass of isophthalic acid, 725 parts by mass of sebacic acid, 154 parts by mass of ethylene glycol, 720 parts by mass of neopentyl glycol and 0.15 parts by mass of dioctyltin dilaurate were charged, and the internal temperature was maintained at 260 ℃ while slowly heating so that the upper temperature of the rectifying tube did not exceed 100 ℃. Xylene was refluxed at 250 ℃ by adding xylene to the mixture at an acid value of 5mgKOH/g using a moisture separator, and the reaction was continued until the acid value was 2mgKOH/g or less. The pressure was reduced to 1333Pa or less, xylene was removed by keeping for 1.5 hours, and the esterification reaction was terminated to obtain an intermediate polyester polyol having an acid value of 1 mgKOH/g. The solution was dissolved and diluted with ethyl acetate to prepare a solution having a solid content of 60% by mass. Further, 4 parts by mass of isophorone diisocyanate and 0.025 parts by mass of dioctyltin dilaurate were added to 100 parts by mass of the obtained intermediate polyester polyol, and the resulting mixture was heated to 80 ℃ to conduct urethanization until substantially no free NCO groups were present, thereby obtaining a polyester urethane polyol having a hydroxyl value of 7 (hereinafter, this is abbreviated as "polyol (x 6)"). The number average molecular weight (Mn) of the polyester urethane polyol is about 9000.
Example 5 preparation of polyisocyanate composition (y1) [ polyisocyanate + Compound having Tetrahydrophthalic anhydride skeleton (c3 ]
15 parts by mass of an isocyanate compound (functional group number: 3-4) of isophorone diisocyanate, 49 parts by mass of trimethylolpropane/adduct of xylylene diisocyanate (TAKENATE D-110N manufactured by Mitsui chemical Co., Ltd.), 3a,4,5,7 a-tetrahydro-7-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -1, 3-iso-benzofurandione [ SP value: 29.1 (J/cm) was put into a flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube3)1/2Acid value 849mgKOH/g]3 parts by mass and 33 parts by mass of methyl ethyl ketone, and the mixture was heated to 60 ℃ and stirred for 1 hour to obtain a polyisocyanate composition (y 1)).
Example 6 preparation of polyisocyanate composition (y2) [ polyisocyanate + Compound having Tetrahydrophthalic anhydride skeleton (c3 ]
Into a flask equipped with a stirrer, a thermometer and a nitrogen gas inlet, 30 parts by mass of isophorone diisocyanate, 32 parts by mass of trimethylolpropane adduct of xylylene diisocyanate ("TAKENATE D-100N" manufactured by Mitsui chemical Co., Ltd.), 3a,4,5,7 a-tetrahydro-7-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -1, 3-isobenzofurandione [ SP value 29.1 (J/cm)3)1/2Acid value 849mgKOH/g]1 part by mass and 37 parts by mass of methyl ethyl ketone, and the mixture was heated to 60 ℃ and stirred for 1 hour to obtain a polyisocyanate composition (y 2)).
Synthesis example 3 (production of polyol (x7) (polyester polyol))
198 parts by mass of terephthalic acid, 162 parts by mass of isophthalic acid, 171 parts by mass of adipic acid, 127 parts by mass of ethylene glycol, 159 parts by mass of diethylene glycol, and 0.14 part by mass of dibutyltin dilaurate were charged into a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, a rectifying tube, a water separator, and the like, and the internal temperature was maintained at 250 ℃ while slowly heating so that the upper temperature of the rectifying tube did not exceed 100 ℃. Xylene was refluxed at 240 ℃ by adding xylene when the acid value was 2.5mgKOH/g, and the reaction was continued until the acid value was 1.5mgKOH/g or less. The pressure was reduced to 1333Pa or less, the reaction was maintained for 1.5 hours, xylene was removed, and the esterification reaction was terminated to obtain a polyester polyol having a number average molecular weight (Mn) of about 4000 (hereinafter, this will be abbreviated as "polyol (x 7)", which was dissolved and diluted with ethyl acetate to prepare a solution having a solid content concentration of 75 mass%.
Comparative example 1 (production of polyol composition (x 8))
198 parts by mass of terephthalic acid, 162 parts by mass of isophthalic acid, 171 parts by mass of adipic acid, 127 parts by mass of ethylene glycol, 159 parts by mass of diethylene glycol, and 0.14 part by mass of dibutyltin dilaurate were charged into a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, a rectifying tube, a water separator, and the like, and the internal temperature was maintained at 250 ℃ while slowly heating so that the upper temperature of the rectifying tube did not exceed 100 ℃. Xylene was refluxed at 240 ℃ by adding xylene when the acid value was 2.5mgKOH/g, and the reaction was continued until the acid value was 1.5mgKOH/g or less. The pressure was reduced to 1333Pa or less, xylene was removed by keeping for 1.5 hours, and the esterification reaction was terminated to obtain a polyester polyol having a number average molecular weight of about 6000.
A styrene-maleic anhydride copolymer ("SMA 1000" manufactured by Cray Valley, styrene/maleic anhydride-1/1 copolymer having a molecular weight of 5500 and a SP value of 31.4 (J/cm) was added thereto in a proportion of 5.3 parts by mass in terms of solid content to 100 parts by mass of the polyester polyol3)1/2) Further, the solid content was adjusted to a 75 mass% solution by dissolving and diluting the polyol in ethyl acetate to obtain a polyol composition (hereinafter, this will be abbreviated as "polyol composition (x 8)". ).
Examples 7 to 14 and comparative examples 2 to 3
The main agent and the curing agent were mixed in accordance with the compositions shown in table 1 or table 2, and the solid content concentration was adjusted with ethyl acetate as shown in table 1 or table 2 to prepare adhesives a to J. Next, the following test for the effect of preventing the disappearance of aluminum vapor deposition and the test for evaluating the laminate appearance were carried out.
In tables 1 and 2, "polyisocyanate (y 3)" is an adduct-type polyisocyanate (ethyl acetate solution, nonvolatile content of 75 mass%) obtained by adding 3 moles of toluene diisocyanate to 1 mole of trimethylolpropane, and "polyisocyanate (y 4)" is a modified product of propylene glycol of methylene diisocyanate (ethyl acetate solution, nonvolatile content of 75 mass%, viscosity at 25 ℃ of 1500 to 2500mPa · s, NCO content of 3.4 mass%).
(test for resistance to Evaporation disappearance)
Using a test laminator (manufactured by MUSASHINO Corporation), the coating amount was 3.0g/m2The composition (1) was applied to an OPP (biaxially oriented polypropylene) film printed with a clear ink and a blue ink, dried to remove the solvent, and then laminated with an aluminum-deposited surface of VMPET (aluminum-deposited PET), and further applied at a coating weight of 3.0g/m2The above method was used to laminate a LLDPE film to prepare a laminate.
Subsequently, the composite film was cured at 40 ℃ for 3 days to cure the adhesive coating film, thereby obtaining a 3-layer composite film of OPP film/adhesive/VMPET/adhesive/LLDPE film. The following materials were used for the film and the ink.
OPP film: toyo Boseki PYLEN FILM-OT P216120 μm
VMPET film: TORAY ADVANCED FILM Co., Ltd. VM-PET 131012 μm
LLDPE films: TUX-HC 60 μm manufactured by Tohcello Co., Ltd
The ink used:
UNIVURE NT R507 ゲンショクアイ K1 manufactured by DIC (blue ink) Inc "
"XS-824R 794 white K1" manufactured by DIC (white ink) Inc.) "
The cured composite film was used to prepare a 120mm × 120 mm-sized pouch, and the pouch was filled with a resin having a mass ratio of 1: 1: 1 simulated food prepared from edible vinegar, salad oil, and meat sauce 70 g. The produced pouches were subjected to boiling sterilization treatment at 98 ℃ for 60 minutes, stored in a 50 ℃ incubator for 6 months, and visually evaluated for the appearance of a single color and blue ink portion.
○ no change in appearance
X: aluminum evaporation disappearance
(lamination appearance confirmation test)
The adhesives prepared in the examples and comparative examples were laminated at a coating rate of 250 m/min using a DL-600DX dry laminator (manufactured by Orient sogyo co., ltd.) using the same base film and the same coating amount as those used in the "aluminum vapor deposition disappearing prevention test", to obtain a 3-layer composite film of OPP film/adhesive/VMPET/adhesive/LLDPE film. The appearance of the composite film immediately after lamination was visually confirmed.
○, indicates no entrained bubbles.
X: with an entrainment bubble.
[ Table 1]
[ Table 2]
Claims (7)
1. A urethane adhesive comprising, as essential components:
a polyol (a) selected from the group consisting of a polyester polyol (a1), a polyester urethane polyol (a2), and a polyether urethane polyol (a 3);
a polyisocyanate (B); and
a copolymer (c1) of an aromatic vinyl and maleic anhydride, and 3a,4,5,7 a-tetrahydro-7-methyl-5- (tetrahydro-2, 5-dioxo-3-furyl) -1, 3-iso-benzofurandione or 2, 2-di (hydroxymethyl) propionic acid as additive components, wherein the additive components have an SP value of 20 to 32 (J/cm)3)1/2And an acid value of 250 to 1000mgKOH/g,
and the additive component is contained in a proportion of 0.01 to 1.5 parts by mass relative to 100 parts by mass of the polyol (A),
the polyol (A) and the polyisocyanate (B) are used in such a ratio that the equivalent ratio of isocyanate groups in the polyisocyanate (B) to hydroxyl groups in the polyol (A) [ isocyanate groups/hydroxyl groups ] is 1.5 to 2.5.
2. A polyol composition for a urethane adhesive, which comprises a polyol (A) selected from the group consisting of a polyester polyol (a1), a polyester urethane polyol (a2) and a polyether urethane polyol (a3), a copolymer (c1) of an aromatic vinyl and maleic anhydride as an additive component, in an amount of 0.01 to 1.5 parts by mass per 100 parts by mass of the polyol (A), 3a,4,5,7 a-tetrahydro-7-methyl-5- (tetrahydro-2, 5-dioxo-3-furanyl) -1, 3-iso-benzofurandione or 2, 2-di (hydroxymethyl) propionic acid, and an organic solvent (D), wherein the additive component has an SP value of 20 to 32 (J/cm)3)1/2And an acid value of 250 to 1000mgKOH/g,
wherein the solid content is 50-80% by mass.
3. A polyisocyanate composition for a urethane adhesive, which comprises as essential components: a polyisocyanate (B); a copolymer of aromatic ethylene and maleic anhydride (c1), 3a,4,5,7 a-tetrahydro-7-methyl-5- (tetrahydro-2, 5-dioxo-3-furanyl) -1, 3-iso-benzofurandione or 2, 2-di (hydroxymethyl) propionic acid as additive components; and an organic solvent (D), wherein the SP value of the additive component is 20 to 32 (J/cm)3)1/2And an acid value of 250 to 1000mgKOH/g,
wherein the solid content is 50-80% by mass.
4. The polyisocyanate composition for a urethane adhesive according to claim 3, wherein the polyisocyanate composition for a urethane adhesive is used together with a polyol (A) selected from the group consisting of a polyester polyol (a1), a polyester urethane polyol (a2) and a polyether urethane polyol (a3), and the additive component is contained in a proportion of 0.01 to 1.5 parts by mass relative to 100 parts by mass of the polyol (A) used together.
5. A cured product obtained by curing the urethane adhesive according to claim 1.
6. A laminated film obtained by applying the urethane adhesive according to claim 1 to a first base film, laminating a second base film on the applied surface, and curing the adhesive layer.
7. The laminate film according to claim 6, wherein the first substrate film is a metal foil or a metal vapor-deposited film, and the second substrate film is a non-stretched polypropylene film or a low-density polyethylene film.
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| JP2016-124577 | 2016-06-23 | ||
| JP2016124577 | 2016-06-23 | ||
| PCT/JP2017/020421 WO2017221661A1 (en) | 2016-06-23 | 2017-06-01 | Urethane-based adhesive, polyol composition for urethane-based adhesive, polyisocyanate composition for urethane-based adhesive, hardened material of urethane-based adhesive, and lamination film |
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| CN109462992A CN109462992A (en) | 2019-03-12 |
| CN109462992B true CN109462992B (en) | 2020-04-17 |
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| JP (1) | JP6278166B1 (en) |
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| WO2020026935A1 (en) * | 2018-08-01 | 2020-02-06 | Dic株式会社 | Adhesive composition and surface protection film |
| JP7206888B2 (en) * | 2018-12-19 | 2023-01-18 | Dic株式会社 | Reactive adhesives, laminated films, and packages |
| JP7439391B2 (en) * | 2019-04-19 | 2024-02-28 | ａｒｔｉｅｎｃｅ株式会社 | Adhesive composition and manufacturing method thereof, laminated film and packaging body |
| JP7088138B2 (en) * | 2019-07-29 | 2022-06-21 | 凸版印刷株式会社 | Laminates and packaging bags |
| JP7231095B2 (en) * | 2019-07-29 | 2023-03-01 | 凸版印刷株式会社 | Laminates and packaging bags |
| JP7443763B2 (en) * | 2019-12-25 | 2024-03-06 | ａｒｔｉｅｎｃｅ株式会社 | Adhesive composition and laminate |
| EP4159639A4 (en) * | 2020-06-02 | 2024-06-26 | artience Co., Ltd. | Two-pack type curable adhesive, multilayer body and package |
| TW202323471A (en) * | 2021-12-14 | 2023-06-16 | 日商Ｄｉｃ股份有限公司 | Adhesive, laminate, and packaging material |
| CN115820195A (en) * | 2022-08-15 | 2023-03-21 | 杭州星华反光材料股份有限公司 | Polyurethane glue for high-brightness reflective material and application thereof |
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| CN102102005A (en) * | 2010-12-13 | 2011-06-22 | 嘉兴禾欣化学工业有限公司 | Preparation method of environmentally-friendly aqueous polyurethane adhesive |
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| JP4771276B2 (en) * | 2005-03-31 | 2011-09-14 | 日本ポリウレタン工業株式会社 | Laminating adhesive |
| JP6210306B2 (en) * | 2013-12-19 | 2017-10-11 | Dic株式会社 | Solvent-free two-component curable laminate adhesive composition |
| JP6617916B2 (en) * | 2015-11-19 | 2019-12-11 | Dic株式会社 | Polyol composition for solventless adhesive, solventless adhesive, and laminated film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1445261A (en) * | 2002-03-19 | 2003-10-01 | 罗姆和哈斯公司 | Carbamate polymer composition |
| CN1467259A (en) * | 2002-06-10 | 2004-01-14 | ��������ķ������ | Urethane polymer compositions |
| JP2005290285A (en) * | 2004-04-02 | 2005-10-20 | Toyo Ink Mfg Co Ltd | Adhesive for dry laminate for metal film |
| CN101649039A (en) * | 2008-08-15 | 2010-02-17 | 段友芦 | Aqueous polyurethane dispersion with high solid content and low activation temperature, preparation method and application thereof |
| CN102102005A (en) * | 2010-12-13 | 2011-06-22 | 嘉兴禾欣化学工业有限公司 | Preparation method of environmentally-friendly aqueous polyurethane adhesive |
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| JPWO2017221661A1 (en) | 2018-06-21 |
| JP6278166B1 (en) | 2018-02-14 |
| CN109462992A (en) | 2019-03-12 |
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