CN111433309B - Reactive adhesive, laminated film, and package - Google Patents
Reactive adhesive, laminated film, and package Download PDFInfo
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- CN111433309B CN111433309B CN201880078089.XA CN201880078089A CN111433309B CN 111433309 B CN111433309 B CN 111433309B CN 201880078089 A CN201880078089 A CN 201880078089A CN 111433309 B CN111433309 B CN 111433309B
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- polyol
- component
- isocyanate
- reactive adhesive
- film
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- 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
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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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Wrappers (AREA)
Abstract
The present invention relates to a reactive adhesive, a laminated film using the same, and a package, wherein the reactive adhesive is a reactive adhesive having a polyol component A and an isocyanate component B, the polyol component A contains a polyester polyol A1, the isocyanate component B contains a polyether isocyanate B1, the polyester polyol A1 is a reaction product of a polyol having a branched structure or a polycarboxylic acid having a branched structure as an essential reaction component and a polycarboxylic acid, the molar ratio of isocyanate groups to hydroxyl groups in the reactive adhesive is 2.5 or more, and the value represented by formula (1) is 0.3% or more. (the mass of the polyol or polycarboxylic acid having a branched structure in the total mass of the polyol component A/(the total mass of the polyol component A)). times.100 (%).
Description
Technical Field
The present invention relates to a reactive adhesive, and a laminated film and a package using the same.
Background
Laminated films (also referred to as laminated films) used for various packaging materials, labels, and the like are laminated with various plastic films, metal foils, paper, and the like to impart designability, functionality, storage stability, convenience, and transportability, and particularly, a package formed by molding the laminated film into a bag shape is used as a package for food, pharmaceuticals, lotions, and the like. As such a laminate film, a laminate film obtained by a dry lamination method, which means: an adhesive (also referred to as a solvent-based laminating adhesive in some cases) dissolved in a volatile organic solvent is applied to the film, and the organic solvent is evaporated and dried while passing through an oven, and another film is attached. As such an adhesive, a reactive two-component laminating adhesive (sometimes referred to as a reactive adhesive, a two-component adhesive, a laminating adhesive, or the like) has been conventionally used.
In general, a package using a laminate film is sealed by a heat sealing process to enclose the contents. However, if the heat resistance of the adhesive used for the laminated film is insufficient during the heat-sealing treatment, peeling may occur at the adhesive interface of the laminated film even if good thermal bonding is performed at the sealing surfaces where the sealing films face each other.
Regarding a package in which a laminated film is heat-sealed, patent document 1 describes that a hot water spray type retort treatment of a hot water spray direct laminated body at high temperature and high pressure is resistant to a hot water spray type retort treatment by using, as an adhesive at the time of lamination, a reactive adhesive containing an isocyanate component containing a polyether polyurethane having an isocyanate group obtained by reacting a polyether diol having a number average molecular weight of 100 to 2000 with 4, 4-diphenylmethane diisocyanate at an NCO/OH molar ratio of 1.2 to 6, and 4, 4-diphenylmethane diisocyanate (a2), and a polyester polyol (japanese: ポリオール) having a weight average molecular weight of 5000 to 50000 or a polyester polyurethane polyol having a weight average molecular weight of 5000 to 50000.
However, this document does not describe any peeling at the adhesive interface of the laminated film after the heat sealing treatment, that is, heat sealing resistance.
In the dry lamination method, the coating of the adhesive on the film is continuously performed until the drying step of the organic solvent and the dry lamination step are performed, and particularly in the drying step, the organic solvent is required to be reliably volatilized in a shorter time. This is not only for shortening the manufacturing time, but also because if the organic solvent remains after lamination, appearance defects may be generated due to air bubbles or the like.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-117801
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a reactive adhesive that has excellent lamination resistance and a small amount of residual solvent after a fixed drying time.
Means for solving the problems
The present inventors have found that the above-mentioned problems can be solved by a reactive adhesive comprising a polyol component A and an isocyanate component B, wherein the polyol component A contains a polyester polyol A1, the isocyanate component B contains a polyether isocyanate B1, the polyester polyol A1 is a reaction product of a polyol having a branched structure (Japanese: poly value アルコール) or a polyol having a branched structure as an essential reaction component and a polycarboxylic acid, and the adhesive contains a specific amount of a branched structure.
A reactive adhesive having a polyester polyol a1 and a polyether isocyanate B1 is disclosed in patent document 1. However, patent document 1 does not describe a relationship between a specific amount of a branched structure contained in an adhesive and heat sealing resistance.
That is, the present invention provides a reactive adhesive comprising a polyol component A and an isocyanate component B, wherein the polyol component A contains a polyester polyol A1, the isocyanate component B contains a polyether isocyanate B1, the polyester polyol A1 is a reaction product of a polyol having a branched structure or a polycarboxylic acid having a branched structure as an essential reaction component and a polycarboxylic acid, the molar ratio of isocyanate groups to hydroxyl groups in the reactive adhesive is 2.5 or more, and the value represented by formula (1) is 0.3% or more.
[ mathematical formula 1]
(the mass of the polyol or polycarboxylic acid having a branched structure in the total mass of the polyol component A/(the total mass of the polyol component A)). times.100 (%) (1)
The present invention also provides a laminated film in which an adhesive layer is laminated between a first plastic film and a second plastic film, wherein the adhesive layer is a layer of the reactive adhesive described above.
The present invention also provides a package formed by molding a laminated film into a bag shape, wherein the laminated film is a laminated film formed by laminating an adhesive layer between a first plastic film and a second plastic film, and the adhesive layer is a layer of the above-described reactive adhesive.
Effects of the invention
The adhesive of the present invention has excellent lamination resistance, and therefore the obtained laminated film does not cause peeling or the like at the adhesive interface after heat-sealing treatment, and has excellent appearance. In addition, the adhesive of the present invention can reliably volatilize the organic solvent in a shorter time and reduce the amount of the residual solvent after the drying and fixing time, and therefore, can shorten the production time and can obtain a laminated film having less appearance defects such as bubbles due to the residual solvent.
Detailed Description
(definition of sentence solvent)
As described above, the reactive adhesive of the present invention is a reactive two-component type laminating adhesive.
In the present invention, an adhesive that cures by a chemical reaction of an isocyanate group and a hydroxyl group is used.
In the present invention, a solvent may be used or not. In the present invention, "solvent" means a volatile organic solvent having high solubility capable of dissolving the polyisocyanate and the polyhydroxy substance used in the present invention, "solvent-type" means a case containing such a high-solubility organic solvent, and "solvent-free" means a case not containing such a high-solubility organic solvent. Specific examples of the highly soluble organic solvent include: toluene, xylene, dichloromethane, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, Methyl Ethyl Ketone (MEK), cyclohexanone, toluene, xylene, n-hexane, cyclohexane, and the like. Among them, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are known as organic solvents having particularly high solubility.
When a low viscosity or the like is required, the reactive adhesive of the present invention can be diluted with the above-mentioned organic solvent having a high solubility as appropriate depending on the desired viscosity. In this case, either the polyhydroxy material component a or the isocyanate component B may be diluted, or both may be diluted. Examples of the organic solvent used in this case include methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, Methyl Ethyl Ketone (MEK), cyclohexanone, toluene, xylene, n-hexane, cyclohexane, and the like. Among them, ethyl acetate and Methyl Ethyl Ketone (MEK) are preferable, and ethyl acetate is particularly preferable, from the viewpoint of solubility. The organic solvent is diluted and used so as to be adjusted to a solid content in the range of about 20 to 60 mass% depending on the desired viscosity.
In order to achieve a low viscosity of the adhesive of the present invention, a solvent having a boiling point of 200 ℃ or higher, which contains a carbonyl group having no hydroxyl group, such as triacetin or propylene carbonate, may be used. The amount of the organic solvent having a high boiling point is usually about 0.1 to 10% by mass, depending on the viscosity and the physical properties of the coating film.
The reactive adhesive of the present invention is a reactive adhesive comprising a polyol component A and an isocyanate component B, wherein the polyol component A contains a polyester polyol A1, the isocyanate component B contains a polyether isocyanate B1, the polyester polyol A1 is a reaction product of a polyol and a polycarboxylic acid, the polyol and the polycarboxylic acid having a branched structure as essential reaction components, the molar ratio of isocyanate groups to hydroxyl groups in the reactive adhesive is 2.5 or more, and the value represented by formula (1) is 0.3% or more.
[ mathematical formula 2]
(the mass of the polyol or polycarboxylic acid having a branched structure in the total mass of the polyol component A/(the total mass of the polyol component A)). times.100 (%) (1)
(branched structure)
In the present invention, examples of the branched structure include: a structure in which a branched structure is introduced into a main skeleton of a resin by using an alcohol having 3 or more functions or a polycarboxylic acid having 3 or more functions or an acid anhydride thereof as a raw material polyol or a polycarboxylic acid.
Examples of the alcohol having 3 or more functions used in the present invention include: and 3-or 4-functional aliphatic alcohols such as glycerin, trimethylolpropane and pentaerythritol.
Further, examples of the 3-or more-functional polycarboxylic acid or anhydride thereof include: aliphatic tribasic acids such as 1,2, 5-hexanetricarboxylic acid and 1,2, 4-cyclohexanetricarboxylic acid; aromatic tribasic acids such as trimellitic acid, trimellitic anhydride, 1,2, 5-benzenetricarboxylic acid, 2,5, 7-naphthalenetricarboxylic acid and anhydrides thereof.
As described above, in the present invention, the value represented by formula (1) is 0.30% or more, particularly preferably 0.40% or more, and more preferably 0.45% or more. The upper limit is 1.00%, and more preferably 0.55% or less.
The value represented by the general formula (1) represents the proportion of the branched structure in the total mass of the polyol component A. By setting the range, the heat seal resistance, which is the effect of the present invention, can be improved.
(polyol component A polyester polyol A1)
The polyester polyol a1 used in the present invention is not particularly limited except that it contains the above-mentioned polyol having a branched structure or polycarboxylic acid having a branched structure as an essential reaction component, and a polyester polyol a1 which is a reaction product of a known polyol and polycarboxylic acid can be used. Specifically, examples thereof include: a polyester (I-A-1 a) which is a reaction product between a ring-opening polymerization reaction product of a cyclic ester compound (hereinafter: apply material) and a polyhydric alcohol, and a polyester (I-A-1 b) which is a reaction product between a polyhydric alcohol and a polycarboxylic acid or an acid anhydride thereof.
Here, as the former cyclic ester compound, which can be used as the polyester (I-A-1 a) which is a reaction product between a polyol and a ring-opening polymerization reaction product of the cyclic ester compound, there can be mentioned: propiolactone, butyrolactone, epsilon-caprolactone, sigma-valerolactone, beta-methyl-sigma-valerolactone, and the like.
On the other hand, in the production of the polyester (I-A-1 a), as the polyol to be reacted with the ring-opening polymerization reaction product of the cyclic ester compound, specifically, a compound having 2 hydroxyl groups, there can be mentioned: chain 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, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and bishydroxyethoxybenzene; alicyclic diols such as 1, 4-cyclohexanediol and 1, 4-cyclohexanedimethanol; bisphenols such as bisphenol a, bisphenol F, hydrogenated bisphenol a, and hydrogenated bisphenol F; a dimer diol; polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexene in the presence of a polymerization initiator such as the above-mentioned diol.
The polyester polyol (I-A-1 a) can be produced by ring-opening polymerization of a cyclic ester compound at a temperature of 60 to 120 ℃ using the polyol as an initiator.
On the other hand, the polyol used in the production of the polyester (I-A-1 b) which is a reaction product between a polyol and a polycarboxylic acid or an acid anhydride thereof is specifically a compound having 2 hydroxyl groups, and examples thereof include: chain aliphatic diols such as ethylene glycol, propylene glycol, 1, 3-propanediol, 2-methyl-1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutylene glycol, butylethylpropylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and bishydroxyethoxybenzene; alicyclic diols such as 1, 4-cyclohexanediol and 1, 4-cyclohexanedimethanol; 3-or 4-functional aliphatic alcohols such as glycerin, trimethylolpropane and pentaerythritol; bisphenols such as bisphenol a, bisphenol F, hydrogenated bisphenol a, and hydrogenated bisphenol F; a dimer diol; polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexene in the presence of a polymerization initiator such as the above-mentioned diol.
Examples of the polycarboxylic acid or anhydride thereof to be reacted with the above-mentioned polyol include: acyclic aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, and fumaric acid; alicyclic dicarboxylic acids such as 1, 3-cyclopentanedicarboxylic acid and 1, 4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, 1, 4-naphthalenedicarboxylic acid, 2, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and 1, 2-bis (phenoxy) ethane-p, p' -dicarboxylic acid, and anhydrides thereof.
In the present invention, among the polyester polyols A1, the polyester (I-A-1 b) which is a reaction product between a polyhydric alcohol and a polycarboxylic acid or an acid anhydride thereof is preferred.
The hydroxyl value of the polyester polyol (I-A-1 b) is preferably in the range of 5 to 30mgKOH/g, more preferably in the range of 16 to 24 mgKOH/g.
The polyester (I-A-1 b) preferably has a weight average molecular weight (Mw) in the range of 5,000 to 30,000. That is, when the weight average molecular weight (Mw) is 5,000 or more, the heat seal resistance is good. On the other hand, when the weight average molecular weight (Mw) is 30,000 or less, the appearance after lamination is good. Further, the polyester (I-A-1 b) preferably has a weight average molecular weight (Mw) in the range of 10,000 to 20,000 and a molecular weight distribution (Mw/Mn) in the range of 2.0 to 3.5.
Further, examples of the method for producing the polyester (I-A-1 b) include: a method for producing a polyester polyol by reacting a polyhydric alcohol with a polycarboxylic acid or an acid anhydride thereof in the presence of an esterification catalyst at a temperature of 150 to 270 ℃.
In the present application, the polyester polyurethane polyol (I-a-2) which is a polyol obtained by reacting a polyfunctional isocyanate compound with the polyester polyol a1 described above may be used as the polyester polyol a1, or may be used in combination.
Examples of polyisocyanate compounds which are reacted with the polyester polyol A1 include: aliphatic diisocyanates such as butane-1, 4-diisocyanate, hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, and 2,4, 4-trimethylhexamethylene diisocyanate; aromatic aliphatic diisocyanates such as xylylene diisocyanate and tetramethyl-m-xylylene diisocyanate;
alicyclic diisocyanates such as cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4, 4 '-diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, isopropylidenedicyclohexyl-4, 4' -diisocyanate, norbornane diisocyanate and the like;
aromatic diisocyanates such as 1, 5-naphthalene diisocyanate, 4' -diphenylmethane diisocyanate, 4' -diphenyldimethylmethane diisocyanate, 4' -dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate;
an adduct-type polyisocyanate compound having a urethane bond site in the molecule, and a urethane-type polyisocyanate compound having an isocyanurate ring structure in the molecule.
The adduct-type polyisocyanate compound having a urethane bond site in the molecule can be obtained by, for example, reacting the various diisocyanate compounds described above with a polyol. The polyols used as the raw material of such adduct type polyisocyanate include: linear aliphatic diols such as ethylene glycol, propylene glycol, 1, 3-propanediol, 2-methyl-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, methyl pentanediol, dimethyl butanediol, butyl ethyl propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and bishydroxyethoxybenzene; alicyclic diols such as 1, 4-cyclohexanediol and 1, 4-cyclohexanedimethanol.
The urethane polyisocyanate compound having an isocyanurate ring structure in its molecule includes the urea ester compounds of the various diisocyanate compounds described above, and particularly preferably the urea ester compound of the aliphatic diisocyanate. In addition, from the viewpoint of easily adjusting the viscosity of the adhesive composition to a viscosity suitable for application, a combination of the diisocyanate compound and a urethane product of the diisocyanate compound is preferable. In this case, the mass ratio [ diisocyanate compound/uronate ester ] of the two is preferably in the range of 50/50 to 5/95, more preferably in the range of 40/60 to 10/90, and particularly preferably in the range of 30/70 to 15/85, from the viewpoint of providing a resin composition which has excellent adhesion to a substrate under wet and hot conditions and exhibits a viscosity suitable for coating.
The hydroxyl value of the polyester polyurethane polyol (I-A-2) is preferably in the range of 5 to 30mgKOH/g, more preferably 16 to 24mgKOH/g, from the viewpoint of excellent adhesion to substrates under moist heat conditions.
The polyester polyurethane polyol (I-A-2) preferably has a branched structure in the molecule and a weight average molecular weight (Mw) of 5,000 to 30,000.
The weight average molecular weight (Mw) is particularly preferably in the range of 10,000 to 20,000.
The polyester polyurethane polyol (I-A-2) preferably has a molecular weight distribution (Mw/Mn) of 2.0 to 3.5 as described above. When the molecular weight distribution (Mw/Mn) is within the above range, the effect of improving the adhesion to the substrate due to the low molecular weight component and the effect of increasing the strength of the cured product due to the high molecular weight component are exerted at the same time, and therefore, the substrate adhesion under the hot and humid conditions is excellent and the initial adhesion strength is increased.
Examples of the method for producing the polyester polyurethane polyol (I-A-2) include: a method (method 1) in which a polyester polyol (I-A-1 a) is produced by reacting a product of ring-opening polymerization of a cyclic ester compound with a polyol, and then the polyester polyol (I-A-1 a) is reacted with the polyisocyanate compound in the presence of a urethane-forming catalyst at a temperature in the range of 50 to 100 ℃; or a method (method 2) in which a polyester polyol (I-A-1 b) is obtained by reacting a polyhydric alcohol with a polycarboxylic acid or an acid anhydride thereof in the presence of an esterification catalyst at a temperature ranging from 150 to 270 ℃, and then the polyester polyol (I-A-1 b) is reacted with the polyisocyanate compound in the presence of a carbamation catalyst at a temperature ranging from 50 to 100 ℃.
In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyol (I-a) having an ester structure are values measured by Gel Permeation Chromatography (GPC) under the following conditions.
A measuring device: HLC-8220 GPC, manufactured by Tosoh corporation
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh corporation
+ Tosoh corporation TSK-GEL SuperHZM-Mx 4
A detector: RI (differential refractometer)
Data processing: multi Station GPC-8020 model II, manufactured by Tosoh corporation
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: a tetrahydrofuran solution containing 0.2% by mass in terms of solid content of the resin was filtered through a microfilter (100. mu.l)
(polyol component A other component)
As described above, the polyester polyol a1 is essentially contained in the present invention, but other polyols may be used in combination within a range not impairing the effects of the present invention. For example, a polyhydroxy substance such as a polyester polyhydroxy substance or a polyether polyhydroxy substance having no branched structure can be used in combination. In this case, the amount of the polyester polyol a1 is not particularly limited as long as the branched structure is within the range of the formula (1).
The polyester polyol having no branched structure can be used without particular limitation as long as it is a reaction product of a polyhydric alcohol and a polycarboxylic acid, and 3 or more functional alcohols, or 3 or more functional polycarboxylic acids or anhydrides thereof, which are raw materials having a branched structure in the polyester polyol a1, are not used.
(isocyanate component B polyether isocyanate B1)
The isocyanate component B used in the present invention comprises polyether isocyanate B1.
The polyether isocyanate is an isocyanate which is a reaction product of an isocyanate compound and a polyol having a polyether group.
By using polyether isocyanate, the organic solvent volatility of the obtained adhesive can be improved.
Examples of the isocyanate compound include: aliphatic diisocyanates such as butane-1, 4-diisocyanate, hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, and tetramethylm-xylylene diisocyanate;
alicyclic diisocyanates such as cyclohexane-1, 4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4, 4 '-diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, isopropylidenedicyclohexyl-4, 4' -diisocyanate, norbornane diisocyanate and the like;
aromatic diisocyanates such as 1, 5-naphthalene diisocyanate, 4' -diphenylmethane diisocyanate, 4' -diphenyldimethylmethane diisocyanate, 4' -dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate;
an adduct-type polyisocyanate compound having a urethane bond site in the molecule, and a urethane-type polyisocyanate compound having an isocyanurate ring structure in the molecule.
Specific examples of the polyol having a polyether group include: chain aliphatic diols such as ethylene glycol, propylene glycol, 1, 3-propanediol, 2-methyl-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, and bishydroxyethoxybenzene; alicyclic diols such as 1, 4-cyclohexanediol and 1, 4-cyclohexanedimethanol; polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Among them, polyalkylene glycols having a number average molecular weight of 400 to 1000 are preferable.
The method for reacting the isocyanate compound with the polyol having a polyether group is not particularly limited, and examples thereof include: a method of reacting them in the presence of a carbamation catalyst at a temperature of 50 to 100 ℃. The end point of the reaction can be determined by measuring the isocyanate content of the reaction product.
(isocyanate component B other Components)
As described above, in the present application, polyether isocyanate B1 is essentially contained, but other isocyanates may be used in combination within a range not impairing the effects of the present invention. For example, an isocyanate having no polyether group can be used in combination. As such an isocyanate, an isocyanate compound used in the reaction of the polyether isocyanate B1 can be used as appropriate. Among them, tolylene diisocyanate of trimethylolpropane (hereinafter sometimes referred to as TMP) adduct type is preferable. The blending ratio of the polyether isocyanate B1 in this case is preferably in the range of 50.0 to 99.0 mass%, more preferably in the range of 85.0 to 95.0 mass%, relative to the total amount of the isocyanate component B.
Here, the isocyanate (II) functions as a curing agent for the polyhydroxy compound component (I), but when an epoxy compound or a hydroxyl group-containing polycarbonate resin, which will be described later, is used in combination, it can be cured by reacting with the hydroxyl group when the resin contains a hydroxyl group.
(reactive adhesive)
The reactive adhesive of the present invention is also characterized in that the reactive adhesive is blended so that the molar ratio of isocyanate groups to hydroxyl groups in the reactive adhesive is 2.5 or more. If the amount is within this range, the heat-seal resistance can be further improved. The molar ratio is particularly preferably 2.8 or more, and most preferably 3.0 or more. On the other hand, the upper limit is not particularly limited, but is preferably 5.0 or less from the viewpoint of poor curing.
In the present invention, the isocyanate group is added in an excess amount. It is presumed that the isocyanate group which is not completely reacted with the hydroxyl group contained in the polyol component A reacts with moisture to form a urea bond, and contributes further to the heat-seal resistance.
As described above, the reactive adhesive of the present invention contains the polyol component a and the isocyanate component B as essential components, and further, an aliphatic cyclic amide compound may be mixed with any one of the polyol component a and the isocyanate component B or may be blended as the 3 rd component at the time of application.
Examples of the aliphatic cyclic amide compound used herein include delta-valerolactam, epsilon-caprolactam, omega-enantholactam, eta-caprylolactam, beta-propiolactam, and the like. Among them, epsilon-caprolactam is preferable from the viewpoint of excellent effect of reducing the elution amount of low-molecular chemical substances. Further, the amount of the aliphatic cyclic amide compound is preferably in the range of 0.1 to 5 parts by mass per 100 parts by mass of the polyol component a.
The reactive adhesive of the present invention may contain a pigment in combination as required. The pigment that can be used in this case is not particularly limited, and examples thereof include organic pigments and inorganic pigments such as extender pigments described in 1970 edition of paint raw materials (edited by japan paint association), white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, pearl pigments, and the like, and plastic pigments. Specific examples of these colorants include various colorants, and examples of the organic pigment include: various insoluble azo pigments such as benzidine yellow, fast yellow, and lake red 4R; soluble azo pigments such as lake red C, carmine 6B, and date red 10; various (copper) phthalocyanine-based pigments such as phthalocyanine blue and phthalocyanine green; various basic dyeing lakes such as rhodamine lake, methyl violet lake, etc.; 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 beauty and penetration; nigrosine and the like.
Examples of the inorganic pigment include: various chromates such as chrome yellow, zinc chromate, molybdate orange, and the like; various ferrocyanides such as prussian blue; various metal oxides such as titanium oxide, zinc white, velcade yellow (Japanese: マピコエロー), iron oxide, red iron oxide, 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 and mica-like iron oxide pigments coated with metal oxides, and pearlescent pigments; graphite, carbon black, and the like.
As the extender pigment, for example: precipitated barium sulfate, chalk powder, precipitated calcium carbonate, calcium bicarbonate, gypsum rubrum, alumina white, Silica, hydrous micro-powder Silica (white carbon), ultrafine anhydrous Silica (Aerosil), Silica sand (Silica sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess and the like.
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 design properties.
The mass ratio of the pigment used in the present invention is 1 to 400 parts by mass relative to 100 parts by mass of the total of the isocyanate component B and the polyol component a, and is more preferably 10 to 300 parts by mass in view of excellent adhesiveness, blocking resistance and the like.
In addition, an adhesion promoter can also be used in the reactive adhesive of the present invention. Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, aluminum-based coupling agents, and epoxy resins.
Examples of the silane coupling agent include: aminosilanes such as γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethyldimethoxysilane, and N-phenyl- γ -aminopropyltrimethoxysilane; epoxy silanes such as beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma-glycidoxypropyltriethoxysilane; vinyl silanes such as vinyltris (β -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and γ -methacryloxypropyltrimethoxysilane; hexamethyldisilazane, gamma-mercaptopropyltrimethoxysilane, and the like.
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 lactate, tetraoctadecyl orthotitanate, 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 a bisphenol type epoxy resin, a phenol type epoxy resin, a β -methylglycidyl ether of bisphenol, a β -methylglycidyl ether of phenol resin, a cyclic oxirane type epoxy resin, and a resorcinol type epoxy resin, which are generally commercially available.
The reactive adhesive used in the present invention may contain other additives than the above if necessary. Examples of the additives include: leveling agent; inorganic fine particles such as colloidal silica and alumina sol; 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; a reinforcing agent; a plasticizer; a lubricant; a rust inhibitor; a fluorescent whitening agent; an inorganic heat ray absorbent; a fire retardant; an antistatic agent; dehydrating agents and the like.
These pigments, adhesion promoters and additives may be mixed with either the isocyanate component B or the polyol component A, or may be used together as the component 3 at the time of application. Among them, from the viewpoint of workability, it is preferable to prepare a premix in which a pigment, an adhesion promoter and an additive are blended in advance in the polyol component a as the polyol composition for a laminating adhesive of the present invention, and then use it as a reaction type adhesive.
(laminated film)
The laminated film of the present invention is a laminated film in which an adhesive layer is laminated between a first plastic film and a second plastic film, wherein the adhesive layer contains the reactive adhesive. Specifically, the adhesive layer is obtained by applying the reactive adhesive to a first plastic film, laminating a second plastic film on the applied surface, and curing the adhesive layer. Examples thereof include: a method in which the reactive adhesive is applied to the first plastic film by coating with a roll coater, and then the other substrate is attached without a drying step. The coating conditions are such that the coating is heated to 30 to 90 ℃ in a normal roll coater, and the concentration of the binder in the mixture is preferably about 300 to 3000 mPas at 40 ℃. The amount of the coating is preferably 0.5 to 5g/m in terms of solid content2More preferably 0.5 to 3g/m2Can be used from left to right.
Further, a film obtained by gravure-printing or flexographic-printing a printing ink on the first plastic film may be used, and in this case, a good laminated appearance can be exhibited. The printing ink may be solvent-based, aqueous, or active energy ray-curable.
When the reactive adhesive used in the present invention is used, after lamination, the adhesive is cured at normal temperature or under heating for 12 to 72 hours, and practical properties are exhibited.
The plastic film is not particularly limited as long as it is a material generally used in the field of packaging. For example, as the first plastic film, a PET (polyethylene terephthalate) film, a nylon film, an OPP (biaxially oriented polypropylene) film, a K coating film such as polyvinylidene chloride, a base film such as various vapor deposited films, an aluminum foil, and the like are often used. Sealing films such as CPP (non-stretched polypropylene) film, VMCPP (aluminum vapor-deposited non-stretched polypropylene) film, VMPET (aluminum vapor-deposited polyethylene terephthalate) film, LLDPE (linear low density polyethylene) film, LDPE (low density polyethylene) film, HDPE (high density polyethylene) film, and VMLDPE (aluminum vapor-deposited non-low density polyethylene) film are commonly used as the second plastic film.
The thickness of the sealing film is not particularly limited, but is preferably within a range of 10 to 60 μm, more preferably within a range of 15 to 40 μm, in view of processability into a packaging material, heat-sealing resistance and the like. Furthermore, the sealing film can be provided with a slip property and a tearing property of the packaging material by providing the sealing film with irregularities having a height difference of 5 to 20 [ mu ] m.
In the present invention, even if high-speed lamination processing is performed, excellent appearance of the laminated film can be obtained, and for example, in the case of a film structure of a PET (polyethylene terephthalate) film/VMCPP (aluminum vapor deposition non-oriented polypropylene) film, high-speed processing of 200 m/min or more is performed, and in the case of a film structure of OPP/CPP, high-speed processing of 350 m/min or more is performed, good appearance can be obtained.
(packaging body)
The package of the present invention is formed by molding the laminated film into a bag shape, and specifically, the laminated film is formed into a package by heat-sealing treatment. Further, when considering the use as a package, required performance (easy tearability, hand tearability), rigidity required as a package, durability (e.g., impact resistance, pinhole resistance), and the like, other layers may be laminated as necessary. Usually, it is used in conjunction with a base layer, a paper layer, a2 nd sealing layer, a nonwoven fabric layer, and the like. As a method of laminating other layers, a known method can be used. For example, an adhesive layer may be provided between the other layers, and the layers may be laminated by a dry lamination method, a heat sealing method, an extrusion lamination method, or the like. The adhesive of the present invention may be used as an adhesive for laminating other layers, or other one-pack type urethane-based adhesives, epoxy-based adhesives, aqueous dispersions of acid-modified polyolefins, and the like may be used.
Specific examples of the laminate structure include: a first plastic film layer/adhesive layer/second plastic film layer which can be suitably used for general packaging bodies, lid materials, refill containers and the like, a base material layer/adhesive layer/first plastic film layer/adhesive layer/second plastic film layer which uses the first plastic layer as a barrier layer, and a paper container, a second plastic film layer/paper layer/adhesive layer/first plastic film layer/adhesive layer/second plastic film, a second plastic film layer/paper layer/polyolefin resin layer/base material layer/first plastic film layer/adhesive layer/second plastic film layer, a paper layer/first plastic film layer/adhesive layer/sealant layer of a paper cup or the like, a second plastic film layer/adhesive layer/first plastic film layer/adhesive layer/second plastic film layer which can be suitably used for a tube container or the like, and the like. These laminates may have a printing layer, a top coat layer, and the like as necessary.
As the "other layer", the above-mentioned plastic film may be used, and a paper layer such as natural paper and synthetic paper, or a general plastic film may be used.
The "other layer" may contain known additives, stabilizers, such as antistatic agents, easy-adhesion coating agents, plasticizers, lubricants, antioxidants, and the like. In addition, in order to improve adhesion when the film is laminated with another material, the "another 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 pretreatment.
The form of the package of the present invention includes various forms such as a three-sided sealed bag, a four-sided sealed bag, a corner-folded package bag, a pillow-shaped package bag, a mountain-shaped bottomed container, a tetra Pak, a brick-shaped, a tube-shaped container, a paper cup, a lid material, and the like. The package of the present invention may be provided with an easy-opening treatment and resealability unit as appropriate.
The package of the present invention can be industrially used mainly as a package filled with food, lotion, or medicine. Specific applications include liquid detergents for washing, liquid detergents for kitchen use, liquid detergents for bath use, liquid soaps for bath use, liquid shampoos, liquid conditioners, pharmaceutical tablets, and the like. Further, the present invention can also be applied to a 2-time package for packaging the above containers. In particular, the use of the reactive adhesive makes it possible to suitably use the adhesive as a package for food and pharmaceutical products in which elution is a problem.
[ examples ]
The present invention will be described in detail with reference to examples and comparative examples. In the examples, "part" and "%" are based on mass unless otherwise specified.
Synthesis example 1[ Synthesis of polyol component A1 ]
31.13 parts by mass of ethylene glycol, 294.00 parts by mass of diethylene glycol, 3.5 parts by mass of trimethylolpropane, 102.08 parts by mass of terephthalic acid, 153.11 parts by mass of isophthalic acid and 27.86 parts by mass of adipic acid were charged into a reaction vessel, heated to 260 ℃ under stirring in a nitrogen stream, held for 1 hour, and then cooled to 240 ℃ to perform an esterification reaction. When the acid value is below 5mgKOH/g, slowly reducing the pressure in the reaction vessel, under 1mmHg, 200-240 ℃ reaction for 1 hours, get the acid value of 1.2mgKOH/g polyester polyhydroxy material resin.
The obtained polyester polyol resin was diluted with ethyl acetate to have a solid content of 70%, cooled to 80 ℃ and added with 13.97 parts by mass of toluene diisocyanate (product name: Cosmonate T-80 mitsui chemical company), urethane reaction was carried out at 70 to 80 ℃, and the resulting mixture was diluted with ethyl acetate again to obtain a polyester polyurethane polyol resin having a solid content of 70% (this was designated as polyol component a 1).
Synthesis example 2[ Synthesis of polyol component A2 ]
31.13 parts by mass of ethylene glycol, 294.00 parts by mass of diethylene glycol, 2.39 parts by mass of glycerol, 102.08 parts by mass of terephthalic acid, 153.11 parts by mass of isophthalic acid and 27.86 parts by mass of adipic acid were charged into a reaction vessel, heated to 260 ℃ under stirring in a nitrogen stream and held for 1 hour, and then cooled to 240 ℃ to perform an esterification reaction. When the acid value is below 5mgKOH/g, the reaction vessel is slowly depressurized, and the reaction is carried out at 200 to 240 ℃ under 1mmHg for 1 hour, so as to obtain the polyester polyol resin with the acid value of 1.2 mgKOH/g.
The obtained polyester polyol resin was diluted with ethyl acetate to have a solid content of 70%, cooled to 80 ℃ and added with 13.97 parts by mass of toluene diisocyanate (product name: Cosmonate T-80 mitsui chemical company), urethane reaction was carried out at 70 to 80 ℃, and the resulting mixture was diluted with ethyl acetate again to obtain a polyester polyurethane polyol resin having a solid content of 70% (this was designated as polyol component a 2).
Synthesis example 3[ Synthesis of polyol component A3 ]
33.5 parts by mass of ethylene glycol, 318.25 parts by mass of diethylene glycol, 215.59 parts by mass of terephthalic acid, 176.03 parts by mass of isophthalic acid and 143.29 parts by mass of adipic acid were charged into a reaction vessel, heated to 260 ℃ under stirring in a nitrogen stream and held for 1 hour, and then cooled to 250 ℃ to perform an esterification reaction until the acid value was less than 3 mgKOH/g. Cooling to 240 ℃, slowly decompressing the reaction vessel, reacting for 1 hour at 200-240 ℃ under 1mmHg to obtain the polyester polyol resin with the acid value of 1.5 mgKOH/g. The obtained polyester polyol resin was diluted with ethyl acetate to have a solid content of 75% (this was taken as polyol component A3).
Synthesis example 3[ Synthesis of isocyanate component B1 ]
228.66 parts of ethyl acetate and 260.66 parts by mass of 4', 4-methylene diisocyanate were charged into a reaction vessel, and the temperature was raised to 75 ℃ under stirring in a nitrogen stream, 85.85 parts by mass of polypropylene glycol having a number average molecular weight of about 400 and 339.46 parts by mass of polypropylene glycol having a number average molecular weight of about 700 were added to carry out a urethanization reaction at 70 to 80 ℃. The reaction was continued until the NCO% became 2.6 to 3.2% and the viscosity became constant within S-V, and 95.48 parts by mass of Trimethylolpropane (TMP) -adduct type tolylene diisocyanate (product name Desmodur L-75, manufactured by Bayer Urethane Co.) was added thereto and sufficiently stirred to obtain isocyanate component B1 having a solid content of 75%.
(examples and comparative examples)
Reactive adhesives were obtained according to the combinations in table 1.
(evaluation method)
[ compatibility of polyol component with polyisocyanate component ]
The reactive adhesives blended in the combinations of examples and comparative examples were left at 25 ℃ for 30 minutes. Then, whether the separation into two layers is confirmed.
Does not separate into two layers, and the liquid is clarified
Does not separate into two layers, and the liquid is turbid
Separate into two layers
[ evaluation of Heat seal Strength ]
A nylon film (Unitika, EMBLEM ON 15 μm) was coated with a reactive adhesive (solid content: 3 g/m) blended in combination with each of the examples and comparative examples2) After drying the solvent with a dryer, a linear low-density polyethylene film (LLDPE film; manufactured by Tohcello corporation; TUX HC-60 μm) was aged at 40 ℃ for 72 hours to obtain a laminated film.
The sealing film surfaces of the obtained 2 laminated films were adhered to each other, and the adhesion was carried out at 180 ℃ and 1kgf/cm using a sealing bar having a width of 1cm21-second heat-seal treatment as a sample for heat-seal resistance.
The peeling speed was set to 300 mm/min at an atmosphere temperature of 25 ℃ using a tensile tester manufactured by shimadzu corporation, both ends of the sample for heat seal resistance were subjected to tensile measurement, and the peak value of the tensile strength at this time was defined as the heat seal resistance strength.
The unit of the heat-seal resistance strength was N/15 mm.
[ film State after measurement of Heat seal resistance Strength ]
When the heat seal resistance strength was measured, the film itself was broken after the peak of the strength was exhibited, and the film was broken, and the film was not broken and the laminate layer was peeled off, which was indicated by "x".
The adhesive layer exhibits strong adhesion at break and is a physical property capable of withstanding practical use, and the adhesive layer itself exhibits weak property not withstanding practical use.
[ appearance of coating ]
A polyethylene terephthalate film (hereinafter, abbreviated as "PET film") having a pattern gravure-printed with a printing ink (yellow R794 white in "Finart F407B" manufactured by DIC) was laminated with a reactive adhesive obtained by combining the examples and comparative examples in a laminator (manufactured by Orient) in such an amount that the solid content became 2.7g/m2The coating was carried out at 250m/min in a left-right manner. The laminate film was laminated to VMPET (aluminum vapor deposited polyethylene terephthalate) after passing through a drying oven, to produce a laminate film.
Immediately thereafter, the laminate appearance was evaluated by visual inspection.
Evaluation ∘: good appearance
Evaluation Δ: the transition portion (Japanese: グラデーション portion) has bubbles
Evaluation x: the solid part has air bubbles
[ amount of residual solvent ]
A biaxially oriented polypropylene film (hereinafter, abbreviated as "OPP film") having a pattern gravure-printed with a printing ink (yellow. R794 white in "Finart F407B" manufactured by DIC) was laminated with a reactive adhesive obtained by combining the examples and comparative examples in a laminator (manufactured by Orient) so that the coating amount was 2.7g/m as a solid content2The coating was carried out at 250m/min in a left-right manner. The film was laminated to VMPET (aluminum vapor deposited polyethylene terephthalate film) in a drying oven (at 55 ℃, 65 ℃ and 75 ℃ in each of 3 zones) to produce a laminated film.
Immediately thereafter, a 0.2m sample was taken2The laminate of (4) was cut into a square of about 1.5cm, placed in a Erlenmeyer flask and sealed, and left to stand in a thermostatic bath at 80 ℃ for 30 minutes, and then a gas was sampled from the head space, and the amount of the residual solvent was measured by gas chromatography (7890A, manufactured by Agilent Technologies).
The results are shown in Table 1.
[ Table 1]
In Table 1, as a commercially available polyisocyanate, trimethylolpropane adduct type toluene diisocyanate was used.
As a result, the reactive adhesive obtained in the examples had no problem in terms of compatibility of the polyol component and the polyisocyanate component, and the obtained laminate film had excellent appearance, exhibited sufficient heat-seal resistance, and had excellent appearance. And the amount of residual solvent is small and excellent.
Comparative example 1 was an example having a small NCO/OH molar ratio, and failed to exhibit sufficient heat seal resistance although the appearance was good.
Comparative example 2 is an example that does not contain polyether isocyanate B1. Although excellent in heat-seal resistance, the appearance was poor and the amount of residual solvent was also significantly large.
Comparative examples 3 and 4 are examples in which the polyester polyol A1 contains no branched component. The heat-sealing resistance was insufficient.
Claims (5)
1. A reactive adhesive comprising a polyol component A and an isocyanate component B, wherein the polyol component A contains a polyester polyol A1, the polyester polyol A1 is a reaction product of a polyol having a branched structure or a polycarboxylic acid having a branched structure as an essential reaction component and a polycarboxylic acid, the molar ratio of isocyanate groups to hydroxyl groups in the reactive adhesive is 2.5 or more, and the value represented by formula (1) is 0.3% or more,
the isocyanate component B is a mixture of a reaction product of a polyether group-containing polyol and an isocyanate, and an adduct-type polyisocyanate compound having a urethane bond site in the molecule or a urethane-type polyisocyanate compound having an isocyanurate ring structure in the molecule, the polyether group-containing polyol being at least one selected from a chain aliphatic diol, an alicyclic diol and a polyalkylene glycol,
(mass of polyol or polycarboxylic acid having a branched structure in the total mass of polyol component A/(total mass of polyol component A)). times.100 (%) (1).
2. The reactive adhesive according to claim 1, wherein the isocyanate component B is a mixture of a reaction product of a polyalkylene glycol having a number average molecular weight of 400 to 1000 and an isocyanate, and trimethylolpropane adduct type tolylene diisocyanate.
3. The reactive adhesive according to claim 1 or 2, wherein the polyester polyol A1 is a reaction product of a polyhydric alcohol and a polycarboxylic acid, the reaction component being trimethylolpropane or glycerol.
4. A laminated film comprising a first plastic film and a second plastic film laminated therebetween with an adhesive layer being a cured layer of the reactive adhesive according to any one of claims 1 to 3.
5. A package obtained by forming a laminated film into a bag shape, the laminated film being a laminated film obtained by laminating an adhesive layer between a first plastic film and a second plastic film, the adhesive layer being a cured layer of the reactive adhesive according to any one of claims 1 to 3.
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| JP2017-238589 | 2017-12-13 | ||
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| PCT/JP2018/043959 WO2019116905A1 (en) | 2017-12-13 | 2018-11-29 | Reactive adhesive, laminated film, and packaging body |
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| JP6928766B2 (en) * | 2019-11-25 | 2021-09-01 | 東洋インキＳｃホールディングス株式会社 | Manufacturing method for packaging materials, packaging containers and recycled base materials |
| WO2021106583A1 (en) * | 2019-11-27 | 2021-06-03 | Dic株式会社 | Reactive adhesive agent, laminate, and package |
| JP6928767B2 (en) * | 2019-12-06 | 2021-09-01 | 東洋インキＳｃホールディングス株式会社 | Packaging material and recycled base material manufacturing method |
| JP7503395B2 (en) | 2020-02-17 | 2024-06-20 | サカタインクス株式会社 | Printing ink composition for laminate and easily tearable laminate |
| JP6915728B1 (en) * | 2020-05-18 | 2021-08-04 | 東洋インキＳｃホールディングス株式会社 | Gas barrier laminating adhesives, laminates and packaging |
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| JP2011202026A (en) * | 2010-03-25 | 2011-10-13 | Kurabo Ind Ltd | Polyurethane foam for flame lamination |
| JP2016117801A (en) * | 2014-12-19 | 2016-06-30 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition, laminate, and production method of laminate |
| CN107001902A (en) * | 2015-03-20 | 2017-08-01 | Dic株式会社 | No-solvent type laminating adhesive, its solidfied material, laminating adhesive glycol composition and stacked film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS63196678A (en) * | 1987-02-09 | 1988-08-15 | Dainippon Ink & Chem Inc | Adhesive composition for laminating films |
| DE4232015A1 (en) * | 1992-09-24 | 1994-03-31 | Bayer Ag | Solvent-free two component polyurethane adhesive systems |
| US8382937B2 (en) * | 2005-02-14 | 2013-02-26 | Henkel Corporation | Laminating adhesives based on triglyceride-derived polyols |
| JP5472525B1 (en) * | 2013-01-22 | 2014-04-16 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition, laminate and method for producing the same |
| CN105705331B (en) * | 2013-08-02 | 2019-01-04 | 巴斯夫欧洲公司 | Multilayer composition for packaging |
-
2018
- 2018-11-29 WO PCT/JP2018/043959 patent/WO2019116905A1/en active Application Filing
- 2018-11-29 JP JP2019522598A patent/JP6620963B2/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011202026A (en) * | 2010-03-25 | 2011-10-13 | Kurabo Ind Ltd | Polyurethane foam for flame lamination |
| JP2016117801A (en) * | 2014-12-19 | 2016-06-30 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition, laminate, and production method of laminate |
| CN107001902A (en) * | 2015-03-20 | 2017-08-01 | Dic株式会社 | No-solvent type laminating adhesive, its solidfied material, laminating adhesive glycol composition and stacked film |
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| WO2019116905A1 (en) | 2019-06-20 |
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