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PH12015501618B1 - Adhesive composition, and laminate and method for manufacturing same - Google Patents

Adhesive composition, and laminate and method for manufacturing same Download PDF

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Publication number
PH12015501618B1
PH12015501618B1 PH12015501618A PH12015501618A PH12015501618B1 PH 12015501618 B1 PH12015501618 B1 PH 12015501618B1 PH 12015501618 A PH12015501618 A PH 12015501618A PH 12015501618 A PH12015501618 A PH 12015501618A PH 12015501618 B1 PH12015501618 B1 PH 12015501618B1
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PH
Philippines
Prior art keywords
adhesive composition
polyol
component
less
diol
Prior art date
Application number
PH12015501618A
Other versions
PH12015501618A1 (en
Inventor
Usa Yuki
Uchiyama Yusei
Sato Yoshihiro
Original Assignee
Toyochem Co Ltd
Toyo Ink Sc Holdings Co Ltd
Toyo Morton Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyochem Co Ltd, Toyo Ink Sc Holdings Co Ltd, Toyo Morton Ltd filed Critical Toyochem Co Ltd
Publication of PH12015501618B1 publication Critical patent/PH12015501618B1/en
Publication of PH12015501618A1 publication Critical patent/PH12015501618A1/en

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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
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • 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
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

Provided is an adhesive composition capable of realizing equal or greater adhesive performance in short-time aging relative to the prior art and that has a long pot life without strict management of the ambient temperature at a low temperature. This adhesive composition includes a polyisocyanate compound (A) and a polyol compound (B), the polyisocyanate compound (A) is a reactive product obtained by reacting 2,4'-diphenylmethane diisocyanate (a1), 4,4'-diphenylmethane diisocyanate (a2), and a polyol having a polyether polyol (a3) as an essential component thereof in an excess of isocyanate groups, and the polyol component (B) has a polyester diol (b1) having a number-average molecular weight of 500 to 3000 as an essential component thereof and furthermore includes a diol (b2) and/or a triol (b3) having a number-average molecular weight of 50 to less than 500.

Description

LT c oC
TW ' DESCRIPTION
ADHESIVE COMPOSITION, AND LAMINATE AND METHOD FOR
MANUFACTURING THE SAME
Technical Field
The present invention relates to adhesive compositions. In addition, the present invention ’ : relates to laminates in which the aforementioned adhesive compositions are used and to methods for manufacturing the laminates. "16 PR P3133
Background Art io
Conventionally, bonding of various types of plastic films with each other or bén ing of a plastic film with a metallized film or a metal foil has been carried out through a dry Tamination method in which a hydroxyl-group/isocyanate-based solvent adhesive is used. However, since the dry lamination method employs an adhesive containing an organic solvent, specialized facilities for suppressing/preventing environmental pollution or a fire are necessary.
In recent years, a demand for simple facilities has led to an increasing demand for adhesives that are free of organic solvents, and studies on a shift to solventless adhesives have been actively carried out.
For example, PTL 1 discloses a solventless adhesive composition for lamination that contains a polyol component (1) and a polyisocyanate component (2) composed of two types of polyisocyanate compounds.
In addition, PTL 2 discloses a solventless lamination adhesive composition that contains a polyol component (1) and a polyisocyanate component (2) essentially containing a trifunctional polyisocyanate compound, that has a branching point concentration within a specific range, and in which the number of moles of a hydroxy! group:the number of moles of an isocyanate group = 1:1 to 1:3.
PTL 3 discloses a solventless adhesive composition that contains a polyol component (A) and an isocyanate component (B) essentially containing isophorone diisocyanate.
PTL 4 discloses a solventless adhesive composition that contains a polyol component (A), a polyisocyanate compound (B), and powders (C) with a specific particle size.
Furthermore, PTL 5 discloses an adhesive composition that contains a polyisocyanate component (a) and a polyol component (b), and the polyisocyanate component (a) contains a
Lo CN 6 monomeric 4,4'-methylene diphenyl diisocyanate (i) and an isocyanate functional prepolymer (ii). The isocyanate functional prepolymer (ii) is a reaction product of a prepolymer reactant mixture containing monomeric 4,4'-methylene diphenyl diisocyanate and at least one polyol, and the at least one polyol includes a triol with an average molecular weight that falls within a predetermined range.
Citation List
Patent Literature
PTL 1: Japanese Unexamined Patent Application Publication No. H8-60131
PTL 2: Japanese Unexamined Patent Application Publication No. 2003-96428
PTL 3: Japanese Unexamined Patent Application Publication No. 2006-57089
PTL 4: Japanese Unexamined Patent Application Publication No. 2011-162579
PTL 5: Japanese Unexamined Patent Application Publication No. 2012-131980
Summary of Invention Technical Problem
As a method for obtaining a laminate by using an adhesive composition, typically employed is a method in which, after a substrate (target to be bonded) is coated with an adhesive composition, a formed adhesive layer is overlaid with another substrate (target to be bonded), and, in that state, curing of the adhesive layer sandwiched between the two substrates is advanced. Hereinafter, the aforementioned process of "advancing curing of an adhesive layer" is referred to as an "aging process."
In the inventions described in PTL 1 to PTL 4, as a polyisocyanate component, specifically, an alicyclic polyisocyanate component or an aliphatic polyisocyanate component is used. An alicyclic polyisocyanate component or an aliphatic polyisocyanate component reacts relatively gradually, and thus the aging process takes 2-5 days at 40-50°C. However, in the market, there is a demand that an adhesive composition, which can exhibit a bonding : performance equivalent or superior to conventional art with an shorter-duration aging than the conventional art, be provided.
As compared to an alicyclic polyisocyanate component or an aliphatic polyisocyanate component, an aromatic polyisocyanate component is highly reactive and is thus suitable for the : object of reducing the aging duration. However, as the reactivity is high, a reaction with a polyol :
: on cc component and a reaction with water in environmental moisture compete with each other; thus, it is necessary to tightly control the environmental humidity during coating, overlaying, and aging to a low humidity in order to achieve a sufficient bonding strength. Therefore, in the market, there is a demand that an adhesive composition be provided that can exhibit equivalent or superior bonding performance with shorter-duration aging than before even when the environmental humidity is not tightly controlled to a low humidity.
Although the invention described in PTL 5 can exhibit bonding performance with relatively short-duration aging, there is a problem in that the viscosity exceedingly increases in a short period of time after a polyol component and a polyisocyanate component have been mixed together, or in other words, the pot life of the adhesive composition is shortened.
The present invention has been made in view of the above background, and it is an object of the present invention to provide an adhesive composition that can exhibit equivalent or superior bonding performance with shorter-duration aging than before even when the environmental humidity is not tightly controlled to a low humidity and that has a long pot life, and to provide a laminate in which the aforementioned adhesive composition is used and a method for manufacturing the laminate.
Solution to Problem
The present invention has been made in view of the above problem, and contains, as a polyisocyanate component (A), a polyisocyanate component derived from two types of aromatic isocyanate and a polyether polyol and contains, as a polyol component (B), a polyol component containing a polyester diol with a specific molecular weight and a diol or triol with a relatively : low molecular weight.
In other words, the present invention relates to an adhesive composition comprising a polyisocyanate component (A) and a polyol component (B), wherein the polyisocyanate component (A) is a reaction product obtained by reacting isocyanate essentially containing 2,4'- diphenylmethane diisocyanate (al) and 4,4'-diphenylmethane diisocyanate (a2) with a polyol essentially containing a polyether polyol (a3) under a condition of excessive isocyanate groups, ] and the polyol component (B) is a polyol composition essentially containing a polyester diol (b1) with a number-average molecular weight of 500 or more and 3,000 or less and further containin g ;
I cc at least one of a diol (b2) with a a vege oleae weight of 50 or more and less than 500 and a triol (b3) with a number-average molecular weight of 50 or more and less than 500.
It is preferable that the adhesive composition according to the present invention include, based on a total of 100 mol% of 2,4'-diphenylmethane diisocyanate (al) and 4,4'- diphenylmethane diisocyanate (a2), 2,4'-diphenylmethane diisocyanate (al) in 10 mol% or more and 60 mol% or less and 4,4'-diphenylmethane diisocyanate (a2) in 40 mol% or more and 90 mol% or less.
In addition, it is preferable that the adhesive composition according to the present invention include, based on 100 mass% of the polyol component (B), the polyester diol (b1) in 60 mass% or more and 99 mass% or less, the diol (b2) and the triol (b3) in combination in 1 mass% or more and 40 mass% or less.
In addition, it is preferable that, based on 100 moles of a hydroxyl group in the polyol component (B), the number of moles of an isocyanate group in the polyisocyanate component (A) be 70 moles or more and 300 moles or less.
In addition, it is preferable that the adhesive composition according to the present invention be of a solventless type.
In addition, it is preferable that the adhesive composition according to the present invention be a lamination adhesive for forming a packaging material.
Furthermore, the present invention relates to a laminate formed by laminating at least two sheet-like substrates by using the adhesive composition according to the present invention.
Furthermore, the present invention relates to a method for manufacturing a laminate by applying the adhesive composition according to the present invention on a first sheet-like substrate to form an adhesive layer, overlaying the adhesive layer with a second sheet-like substrate, and curing the adhesive layer interposed between the two sheet-like substrates.
Advantageous Effects of Invention :
According to the present invention, an excellent effect is obtained that an adhesive composition that can exhibit equivalent or superior bonding performance with shorter-duration i aging than before even when the environmental humidity is not tightly controlled to a low
LC oC humidity and that has a long pot life, a laminate . which the adhesive composition is used, and a method for manufacturing the laminate can be provided.
Description of Embodiments
An adhesive composition according to the present invention includes a polyisocyanate component (A) and a polyol component (B).
The polyisocyanate component (A) is a reaction product obtained by reacting isocyanate essentially containing 2,4'-diphenylmethane diisocyanate (2,4'-diphenylmethane diisocyanate) (al) and 4,4'-diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate) (a2) with a polyol essentially containing a polyether polyol (a3) under a condition of excessive isocyanate REE groups. Hereinafter, 2,4'-diphenylmethane diisocyanate (al) is abbreviated to 2,4'-MDI (al), and 4,4'-diphenylmethane diisocyanate (a2) is abbreviated to 4,4'-MDI (a2) in some cases.
The polyol component (B) is a polyol composition essentially containing a polyester diol (bl) with a number-average molecular weight of 500 or more and 3,000 or less and further containing at least one of a diol (b2) with a number-average molecular weight of 50 or more and less than 500 and a triol (b3) with a number-average molecular weight of 50 or more and less than 500.
With the above composition, an adhesive composition that can exhibit equivalent or superior bonding performance with shorter-duration aging than before even when the environmental humidity is not tightly controlled to a low humidity and that has a long pot life can be provided. Although inclusion of a solvent is not excluded, the adhesive composition according to the present invention is superior in that the adhesive composition can be applied to asolventless type. It is to be noted that a solventless type is the one that substantially does not include a solvent, and those containing a solvent that inevitably remains after the manufacturing process or the like or a small amount of solvent that does not affect the properties are encompassed in the solventless type in the present invention. Hereinafter, the present invention will be described in detail.
The polyisocyanate component (A) includes a blend of a urethane prepolymer that has resulted from a reaction of 2,4'-MDI (al) with a polyol and a urethane prepolymer that has resulted from a reaction of 4,4'-MDI (a2) with a polyol, or/and a urethane prepolymer that has
EE oC resulted from a reaction of 2,4'-MDI (al) and 44-MDI (a2) with a polyol. In addition, the polyisocyanate component (A) may include unreacted 2,4'-MDI (al) or unreacted 4,4'-MDI (a2).
By using 4,4'-MDI (a2) in combination with 2,4'-MDI (al) as the polyisocyanate component (A), sufficient bonding performance can be exhibited even with short-duration aging.
Meanwhile, by using 2,4-MDI (al) in combination with 4,4'-MDI (a2), sufficient bonding performance can be exhibited even with coating/overlaying/aging in a high-humidity environment. In addition, it is preferable that, based on a total of 100 mol% of 2,4'-MDI (al) and 4,4'-MDI (a2), 2,4'-MDI (al) be 10-60 mol% (including the upper limit value and the lower limit value. Hereinafter, the same) and 4,4'-MDI (a2) be 40-90 mol%. By setting the composition ratio of the two types of MDI within the aforementioned ranges, equivalent or superior bonding performance can be exhibited more effectively with shorter-duration aging than before even when the environmental humidity is not tightly controlled to a low humidity.
A polyol forming the polyisocyanate component (A) will be described. The polyol contains the polyether polyol (a3) as an essential component and may additionally contain a polyester polyol. A polyether polyol typically has a lower viscosity in a molten state than a polyester polyol, and thus it is important that the polyether polyol (a3) be essential as a polyol for forming the polyisocyanate component (A), which is a constituent component of the adhesive. Furthermore, by using a polyester polyol in combination, the compatibility with the polyol component (B), which will be described later, can be increased, and the cohesive strength of the adhesive composition can also be increased.
When a polyester polyol is used in combination, based on 100 mass% of the polyol, 30 mass% or less is preferable in consideration of the viscosity of the adhesive composition; 1-30 mass% is more preferable, and 1-20 mass% is even more preferable.
The polyether polyol (a3) can, for example, be a polyether polyol or the like that is obtained by polymerizing an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, with, for example, water and a low-molecular weight polyol such as ethylene glycol, propylene glycol, trimethylolpropane, and glycerin, serving as an initiator. :
As the polyether polyol (a3), in addition to a bifunctional polyether polyol, a trifunctional : polyether polyol or higher can be used. In addition, a plurality of polyether polyols that differ in the number of functional groups can be used in combination. It is preferable that the number- average molecular weight of the polyether polyol (a3) be 100 or more and 5,000 or less. It is to be noted that a plurality of polyether polyols (a3) that differ in the number-average molecular weight can also be used in combination.
I
The polyester polyol to be used in combination can be a polyester polyol or the like that is obtained by reacting a polycarboxylic acid component with a glycol component.
The polycarboxylic acid component can be, for example, polycarboxylic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or their dialkyl esters, or a mixture thereof, The glycol component can be, for example, glycols such as ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3- methyl-1,5-pentanediol, 3,3-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, and polytetramethylene ether glycol, or a mixture thereof.
The polyisocyanate component (A) used in the present invention can be obtained, for example, by reacting a mixture of 2,4'-MDI (al) and 4,4'-MDI (a2) with a polyol essentially containing the polyether polyol (a3). Alternatively, the polyisocyanate component (A) can also be obtained by mixing reaction products obtained by reacting 2,4'-MDI (al) and 4,4'-MDI (a2) each with a polyol essentially containing the polyether polyol (a3). Furthermore, the polyisocyanate component (A) can also be obtained by reacting 2,4'-MDI (al) and 4,4'-MDI (a2) one after another with a polyol essentially containing the polyether polyol (a3).
The polyisocyanate component (A) used in the present invention may be obtained by reacting the aforementioned components under the condition of excessive isocyanate groups, and preferably by reacting the components with the equivalent ratio of an isocyanate group to a hydroxyl group being in a range from more than 1 to 6 or less, and more preferably in a range from 1.5 or more to 4 or less.
By reacting 2,4'-MDI (al) and 4,4'-MDI (a2) with a polyol at an equivalent ratio in the aforementioned range, the polyisocyanate component (A) containing a urethane prepolymer with a suitable number-average molecular weight and an isocyanate group in a suitable amount can be obtained. As a result, when an adhesive composition is obtained by mixing the polyisocyanate : component (A) with the polyol component (B), which will be described later, and a laminate is obtained by using the adhesive composition, a sufficient bonding strength can be obtained.
PEE ( oC
Subsequently, the polyol component (B) heed in the present invention will be described.
As described above, the polyol component (B) essentially contains the polyester diol (b1) with a number-average molecular weight of 500 or more and 3,000 or less, and further contains at least either the diol (b2) with a number-average molecular weight of 50 or more and less than 500 or the triol (b3) with a number-average molecular weight of 50 or more and less than 500. After the present inventors have carried out extensive examinations, it was found that a sufficient bonding strength could not be obtained when the polyester diol (b1) was used alone as the polyol component (B). In addition, it was found that, when the diol (b2) or/and the triol (b3) was/were used as the polyol component (B) without using the polyester diol (bl), not only was the pot life short but a sufficient bonding strength could not be obtained, either. In other words, it was found that, by using the polyester diol (bl) with a specific number-average molecular weight as the polyol component (B) and by also using the diol (b2) or/and triol (b3) with a specific number- average molecular weight, the pot life could be improved while the bonding performance equivalent or superior to that of a conventional adhesive was achieved.
The polyester diol (bl) can be, for example, a polyester diol obtained by reacting polycarboxylic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and - sebacic acid, or their dialkyl esters, or a mixture thereof with glycols such as ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl- 1,5-pentanediol, 3,3-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, and polytetramethylene ether glycol, or a mixture thereof. In addition, the polyester diol (b1) can be a polyester diol or the like obtained by subjecting the aforementioned polycarboxylic acids or their dialkyl esters or a mixture thereof and lactones such as polycaprolactone, polyvalerolactone, and poly(B-methyl-y-valerolactone), to ring-opening polymerization.
By using the polyester diol (b1) with a number-average molecular weight in the aforementioned range, the compatibility with the aforementioned polyisocyanate component (A) that essentially contains polyether polyurethane as a constituent component improves; thus, a transparent adhesive composition can be obtained, and sufficient bonding performance can be exhibited.
The diol (b2) with a number-average molecular weight of 50 or more and less than 500 can be, for example, polyester diol, polyether diol, polyetherester diol, polyesteramide diol, acrylic diol, or polycarbonate diol; low-molecular weight diols such as ethylene glycol, ] propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-
1,5-pentanediol, 3,3-dimethylolheptane, and methyl] 3-propanediol or a mixture thereof.
Among these, in consideration of the reactivity, the low-molecular weight diols are preferable.
The aforementioned polyester diol can be, for example, a polyester diol obtained by reacting dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or their dialkyl esters, or a mixture thereof with, for example, bifunctional glycols such as ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, and polyoxypropylene glycol, or a mixture thereof, or a polyester diol obtained by subjecting lactones such as polycaprolactone, polyvalerolactone, and poly(B-methyl-y-valerolactone), to ring-opening polymerization.
The aforementioned polyether diol can be, for example, a polyether diol obtained by polymerizing an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, with, for example, water and a bifunctional low-molecular weight polyol such as ethylene glycol, and propylene glycol, serving as an initiator.
The aforementioned polyetherester polyol can be, for example, a polyetherester diol obtained by reacting dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, and sebacic acid, or their dialkyl esters, or a mixture thereof with the aforementioned polyether diol.
The aforementioned polyesteramide diol can be obtained by additionally using, for example, aliphatic diamine having an amino group, such as ethylenediamine, propylenediamine, and hexamethylenediamine, as an ingredient in the aforementioned esterification reaction.
An example of the aforementioned acrylic diol can be obtained by copolymerizing hydroxyethyl acrylate, hydroxypropyl acrylate, acrylic hydroxybutyl, or the like, or their corresponding methacrylic acid derivatives or the like, in each of which at least one hydroxyl : group is contained in one molecule, with, for example, acrylic acid, methacrylic acid, or an ester ; thereof.
The aforementioned polycarbonate diol can be obtained, for example, by reacting one or more than one glycol selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-
EE C OC pentanediol, 1,6-hexanediol, 3-methyl-1 Speman 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, and 1,4- cyclohexanedimethanol with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, or phosgene, or the like.
The triol (b3) with a number-average molecular weight of 50 or more and less than 500 can be a polyether triol or castor oil; low-molecular weight triols such as trimethylolpropane and glycerin; or a mixture thereof. Among these, in consideration of the reactivity, the low molecular weight triols or the polyether triol is preferable.
The aforementioned polyether triol can be, for example, a polyether triol obtained by polymerizing an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, by using, for example, a low-molecular weight triol such as trimethylolpropane and glycerin.
It is preferable that the polyol component (B) include, based on 100 mass% of the polyol component (B), the diol (b1) in 60 mass% or more and 99 mass% or less and, the diol (b2) and the triol (b3) in 1 mass% or more and 40 mass% or less in combination. As the composition ratio of the diol (b1) and so on falls within the aforementioned range, sufficient pot life and bonding performance can be exhibited. With regard to a more preferable range, based on 100 mass%o of the polyol component (B), it is more preferable that the diol (b1) be included in 80 mass% or more and 95 mass% or less, and the diol (b2) and the triol (b3) be included in 5 mass% or more and 20 mass% or less in combination.
The polyol component (B) can include, in addition to the diol (bl), the diol (b2), and the triol (b3), another polyol component within a scope that does not hinder the object of the present invention,
With regard to the adhesive composition according to the present invention, based on 100 ; moles of a hydroxyl group in the polyol component (B), it is preferable that the number of moles of an isocyanate group in the polyisocyanate component (A) be 70 moles or more and 300 moles or less. By setting the number of moles to 70 moles or more, a sufficient bonding strength can be secured, and by setting the number of moles to 300 moles or less, an adhesive layer can be formed on a deposition surface in an excellent condition. The upper limit value of a more
Lo C oC preferable range is 250 moles or less, and an oven more preferable range is 230 moles or less.
The lower limit value of a more preferable range is 100 moles or more, and an even more preferable range is 150 moles or more.
It is preferable that the adhesive composition according to the present invention do not contain a solvent. When the flowability of each component is poor, it is preferable that each component be separately heated to an extent that can ensure the flowability and then mixed together. As long as the flowability can be ensured, the components do not need to be heated during mixing.
The viscosity immediately after the polyisocyanate component (A), the polyol component (B), other various additives, which will be described later, and so on are mixed is, at least at a temperature in a temperature range from 25°C to 50°C, preferably 50 mPa-s or more and 5,000 mPa-s or less, and more preferably 100 mPa-s or more and 3,000 mPa-s or less.
It is to be noted that, in the present invention, immediately after mixing means within 5 minutes after homogeneous mixing, and the viscosity is indicated by a value obtained with a B- type viscometer. When the viscosity exceeds 5,000 mPa-s at any temperature within the temperature range from 25°C to 50°C, coating becomes difficult, and it is difficult to ensure favorable working properties; thus, there is a possibility that a favorable coating appearance cannot be obtained even if the coating temperature is raised to 100°C. In addition, when being coated at 100°C or higher, a film is stretched and a pitch shift occurs in a print pattern; thus, there is a tendency that laminating becomes impossible. Meanwhile, when the viscosity is less than 50 mPa-s at any temperature within the temperature range from 25°C to 50°C, sufficient bonding performance cannot be obtained as the initial cohesive strength is weak, or an appearance defect or a warp tends to occur as a coated film does not have a uniform thickness when a substrate is coated with the adhesive.
The adhesive composition according to the present invention can further include, for example, an additive such as an antioxidant, an ultraviolet absorber, a hydrolysis preventing agent, a fungicide, a thickener, a plasticizer, an antifoaming agent, a pigment, and a filler, as needed. In addition, in order to further improve the bonding performance, an adhesion aid such as a silane coupling agent, phosphoric acid, a phosphoric acid derivative, acid anhydride, and adhesive resin, can also be used. In addition, a known catalyst, an additive, and so on for : adjusting a curing reaction can be used.
Although a method for using the adhesive somposition according to the present invention is not particularly limited, the following method can be illustrated as a suitable method.
Specifically, the polyisocyanate component (A) and the polyol component (B) are mixed, and the adhesive composition is applied to a surface of a sheet-like substrate by a solventless laminator.
An application amount of the adhesive composition is selected, as appropriate, in accordance with the type of the substrate or the coating condition, and is typically 1.0 g/m” or more and 5.0 g/m” or less and preferably 1.5 g/m* or more and 4.5 g/m? or less.
Thereafter, a bonding surface of the sheet-like substrate is bonded with another sheet-like substrate, which is subjected to aging at a room temperature or while being heated so as to be cured. In the case of the adhesive composition according to the present invention, the time it takes for aging is approximately one day. In addition, in the case of the adhesive composition according to the present invention, sufficient bonding performance can be exhibited even when the environmental humidity is high during the coating to aging processes.
By laminating sheet-like substrates with the use of the adhesive composition according to the present invention, a laminate can be obtained. As a sheet-like substrate, a plastic film of polyester, polyamide, polyethylene, polypropylene, or the like, a metallized film with a deposit of aluminum, silicon oxide, aluminum oxide, or the like, a metal foil of stainless steel, iron, copper, lead, or the like is used. A combination of such substrates may be a combination of plastic films, a combination of a plastic film and a metallized film or a metal foil.
In the aforementioned PTL 5, as described above, there is a problem in that the pot life of the adhesive composition is short. In PTL 3, it is indicated (52nd and 54th paragraphs and so on) that it is favorable that the polyol component (b) be composed only of a triol. However, a triol is highly reactive as compared to a diol component, and thus it is speculated that the viscosity increases exceedingly in a short period of time after a polyol component and a polyisocyanate component are mixed and the pot life of the adhesive composition is thus shortened. :
Meanwhile, according to the present invention, the polyester diol (b1) with a specific number-average molecular weight and the diol (b2) or/and triol (b3) with a specific number- average molecular weight are used as the polyol component, and the above-described polyol component (B) is used in the above-described polyisocyanate component (A). Thus, an adhesive composition that can exhibit equivalent or superior bonding performance with shorter-duration aging than before even when the environmental humidity is not tightly controlled to a low :
SE c SC humidity and that has a long pot life can be Hi. In particular, in the case of a solventless adhesive, an increase in the viscosity in a short period of time has a great influence on the coating performance and productivity and has thus been a major issue from the industrial perspective. However, according to the adhesive composition according to the present invention, even in the case of a solventless type, as described above, equivalent or superior bonding performance can be exhibited with shorter-duration aging than before even when the environmental humidity is not tightly controlled to a low humidity, and a long pot life can be achieved. <<Examples>>
Hereinafter, the present invention will be described more concretely by examples. In the examples and comparative examples, percentages and parts are all based on mass, unless otherwise indicated.
The number-average molecular weights of a polyether polyol, a polyester diol, and so on were obtained through gel permeation chromatography (GPC). The number-average molecular weight measurement was conducted under the following conditions. Model: TOSOH HLC- 8220GPC, Column: TSKGEL SuperHM-M, Solvent: THF, Solution outflow speed: 0.6 ml per minute, Temperature: 40°C, Detector: differential refractometer, Molecular weight standard: polystyrene.
An acid value and a hydroxyl value are indicated by mg of KOH in 1 g of a polymer polyol. The acid value was measured through neutralization titration by KOH, and the hydroxyl value was measured through acetylation with the use of pyridine and acetic anhydride. In addition, NCO content by percentage is indicated by a mass fraction of an amount of an isocyanate group present in a sample. After adding a toluene solution of excess dibutylamine for a reaction and producing corresponding urea, back titration was carried out through an indicator titration method with the use of a hydrochloric acid standard solution, and the NCO content by percentage was measured. (Synthesis Example 1) 30 parts of bifunctional polypropylene glycol, where propylene oxide was added to : water, with a number-average molecular weight of about 400, 40 parts of bifunctional : polypropylene glycol with a number-average molecular weight of about 2,000, 20 parts of trifunctional polypropylene glycol, where propylene oxide was added to glycerin, with a ee : ta “ : 14- number-average molecular weight of about 400, 40 parts of 4,4'-diphenylmethane diisocyanate, and 60 parts of 2,4'-diphenylmethane diisocyanate were introduced into a reactor and were heated for 3 hours at 70-80°C while being stirred in a stream of nitrogen gas, and thus a urethanization reaction was carried out. Polyether polyurethane polyisocyanate resin having an isocyanate group was obtained. The isocyanate group content was 14.4%. Hereinafter, this resin is referred toas polyisocyanate A-(1). (Synthesis Example 2)
In a similar manner to Synthesis Example 1 except that 4,4'-diphenylmethane diisocyanate: 70 parts and 2,4'-diphenylmethane diisocyanate: 10 parts were used, polyether polyurethane polyisocyanate resin having an isocyanate group was obtained. The isocyanate group content was 11.5%. Hereinafter, this resin is referred to as polyisocyanate A-(2). (Synthesis Example 3)
In a similar manner to Synthesis Example 1 except that 4,4'-diphenylmethane diisocyanate: 76 parts and 2,4'-diphenylmethane diisocyanate: 38 parts were used, polyether polyurethane polyisocyanate resin having an isocyanate group was obtained. The isocyanate group content was 16.5%. Hereinafter, this resin is referrred to as polyisocyanate A-(3). (Synthesis Example 4)
In a similar manner to Synthesis Example 1 except that 4,4'-diphenylmethane diisocyanate: 100 parts was used and 2,4'-diphenylmethane diisocyanate was not used, polyether polyurethane polyisocyanate resin having an isocyanate group was obtained. The isocyanate group content was 14.4%. Hereinafter, this resin is referred to as polyisocyanate A-(4). (Synthesis Example 5)
In a similar manner to Synthesis Example 1 except that 4,4'-diphenylmethane diisocyanate was not used and 2,4'-diphenylmethane diisocyanate: 100 parts was used, polyether polyurethane polyisocyanate resin having an isocyanate group was obtained. The amount of the isocyanate group was 14.4%. Hereinafter, this resin is referred to as polyisocyanate A-(5). (Synthesis Example 6)
In a similar manner to Synthesis Example A-1 except that 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate were not used but isophorone diisocyanate
BE C EE
(IPDI): 90 parts was used instead, polyether polyurethane polyisocyanate resin having an isocyanate group was obtained. The amount of the isocyanate group was 14.6%. Hereinafter, this resin is referred to as polyisocyanate A-(6). [Table 1]
Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 —— sMbien Le Lo Tow To Tw [0 mpl To To To 0 0 w ] en ne ee (Synthesis Example 7) 438 parts of isophthalic acid, 106 parts of ethylene glycol, and 179 parts of neopentyl glycol were introduced into a reactor and were heated to 150°C to 240°C while being stirred in a stream of nitrogen gas, and thus an esterification reaction was carried out. Upon the acid value becoming 1.3 (mgKOH/g), the reaction temperature was adjusted to 200°C, and the interior of the reactor was gradually depressurized. The reaction was then carried out for 30 minutes at 1.3 kPa or less, and polyester diol resin having hydroxyl groups at both terminals and with an acid value of 0.4 (mgKOH/g), a hydroxyl value of 137 (mgKOH/g), and a number-average molecular weight of about 800 was obtained. Hereinafter, this polyol is referred to as a polyol (b1)-1. (Synthesis Example 8) 373 parts of isophthalic acid, 42 parts of terephthalic acid, 109 parts of ethylene glycol, and 182 parts of neopentyl glycol were introduced into a reactor and were heated to 150°C to 240°C while being stirred in a stream of nitrogen gas, and thus an esterification reaction was carried out. Upon the acid value becoming 1.3 (mgKOH/g), the reaction temperature was brought to 200°C, and the interior of the reactor was gradually depressurized. The reaction was then carried out for 30 minutes at 1.3 kPa or less, and polyester diol resin having hydroxyl groups at both terminals and with an acid value of 0.5 (mgKOH/g), a hydroxyl value of 184 (mgKOH/g), and a number-average molecular weight of about 600 was obtained. Hereinafter, this resin is referred to as a polyester diol (b1)-2. (Synthesis Example 9)
Co C Co : ‘ * 16- 298 parts of isophthalic acid, 262 parts of adipic acid, 341 parts of ethylene glycol, and 219 parts of diethylene glycol were introduced into a reactor and were heated to 150°C to 240°C while being stirred in a stream of nitrogen gas, and thus an esterification reaction was carried out.
Upon the acid value becoming 1.3 (mgKOH/g), the reaction temperature was brought to 200°C, and the interior of the reactor was gradually depressurized.
The reaction was then carried out for 30 minutes at 1.3 kPa or less, and polyester diol resin having hydroxyl groups at both terminals and with an acid value of 0.5 (mgKOH/g), a hydroxyl value of 40.7 (mgKOH/g), and a number-average molecular weight of about 2,800 was obtained.
Hereinafter, this resin is referred to as a polyester diol (b1)-3. ! (Synthesis Example 10) 186 parts of isophthalic acid, 383 parts of adipic acid, and 429 parts of neopentyl glycol were introduced into a reactor and were heated to 150°C to 240°C while being stirred in a stream of nitrogen gas, and thus an esterification reaction was carried out.
Upon the acid value becoming 1.3 (mgKOH/g), the reaction temperature was brought to 200°C, and the interior of the reactor was gradually depressurized.
The reaction was then carried out for 30 minutes at 1.3 kPa or less, and polyester diol resin having hydroxyl groups at both terminals and with an acid value of 0.4 (mgKOH/g), a hydroxyl value of 27.3 (mgKOH/g), and a number-average molecular weight of about 4,000 was obtained.
Hereinafter, this resin is referred to as a polyester diol (b1)- 4. (Synthesis Example 11) 310 parts of cis-1,4-cyclohexane dicarboxylic acid and 415 parts of 1,4-cyclohexane dimethanol were introduced into a reactor and were heated to 150°C to 220°C while being stirred ina stream of nitrogen gas, and thus an esterification reaction was carried out.
Upon the acid value becoming 3.0 (mgKOH/g), the reaction temperature was brought to 200°C, and the interior : of the reactor was gradually depressurized.
The reaction was then carried out for 30 minutes at 1.3 kPa or less, and polyester diol resin having hydroxyl groups at both terminals and with an acid value of 2.0 (mgKOH/g), a hydroxy! value of 332 (mgKOH/g), and a number-average ; molecular weight of about 300 was obtained.
Hereinafter, this resin is referred to as a polyester polyol (b2)-1. (Example 1) :
Co C oC 200 parts of polyisocyanate A-(1) obtained in Synthesis Example 1 was introduced into a vessel, and while being stirred in a stream of nitrogen gas, 90 parts of polyester diol (b1)-1 obtained in Synthesis Example 7 and 10 parts of diethylene glycol were added, which were then mixed in a warm water bath at 25°C to obtain a solventless adhesive composition.
The viscosity of this composition at 25°C, which was measured within 5 minutes after the homogeneous mixing, was 2,500 mPa-s.
It is to be noted that the solventless adhesive composition contains 166 moles of an isocyanate group derived from polyisocyanate A-(1) relative to 100 moles of the hydroxyl group in the polyol component. The amount of the isocyanate group relative to 100 moles of the hydroxyl group is obtained as follows.
The amount of the isocyanate group relative to 100 moles of the hydroxyl group = [isocyanate group (eq.)/hydroxyl group (eq.)] x 100 isocyanate group (eq.) = NCO content by percentage (mass%)/(42 x 100) hydroxyl group (eq.) = 56110/hydroxyl value
The NCO content by percentage (mass%) is obtained in accordance with JIS K7301, and the hydroxyl value is obtained in accordance with JIS K1557-1.
The pot life of the obtained solventless adhesive composition was evaluated through the following method. In addition, a laminate was obtained with the use of the obtained solventless adhesive composition in accordance with the following method, and the bonding strength of the laminate and the interface condition of the laminate were evaluated. The results are shown in
Table 2. (Examples 2-11, Comparative Examples 1-8)
Except that the polyisocyanate component (A) and the polyol component (B) shown in
Tables 2 and 3 were used in predetermined ratios, a solventless adhesive composition was obtained through a similar operation to that of Example 1. In addition, the pot life, the bonding strength of the laminate, and the interface condition of the laminate were evaluated in a similar manner to Example 1. The results are sown in Tables 2 and 3.
It is to be noted that, in Examples 4 and 9 in which the polyester diol (b1)-3 with a number-average molecular weight of about 2,800 was used and in Comparative Example 8 in which the polyester diol (b1)-4 with a number-average molecular weight of about 4,000 was used, the polyester diol (b1)-3 and the polyester diol (b1)-3 were each heated to 70°C and then mixed with the polyisocyanate A-(1) and so on in a warm water bath at 25°C, and the viscosity
Sc a ‘ ‘ - 18- within 5 minutes after the mixing was measured with a B-type viscometer. The temperature of the adhesive composition at the time of measurement was about 50°C. <Pot Life>
The solventless adhesive composition obtained in each example or comparative example was encapsulated in a 200 g, 250 mL capacity glass bottle having a lid, and the viscosity after the solventless adhesive composition was kept for 30 minutes in a warm water bath at 50°C was measured with a B-type viscometer, and the pot life was thus examined. The temperature of the adhesive composition at the time of measurement was about 50°C. [Fabrication of Laminate]
The solventless adhesive composition obtained in each example or comparative example whose temperature was adjusted to 50°C was applied on a surface of a PET (polyethylene terephthalate) film (thickness: 12 um) by a solventless test coater at 70°C (application amount: 2.0 g/m?), and this coating surface was overlaid with a deposition surface of an aluminum- deposited unstretched polypropylene film (VMCPP, thickness: 25 um) to obtain a preparatory- stage laminate (pre-laminate). This pre-laminate was subjected to aging for one day or two days, i.e, left undisturbed for a certain time period in an environment where the humidity is 60% RT or 80% RT, and then a laminate was fabricated. For each obtained laminate, the bonding strength and the interface condition of the laminate were observed/measured in the following manner, and the results are shown in Tables 2 and 3. (Bonding Strength)
The laminate was cut into a test piece with a length of 300 mm and a width of 15 mm.
With the use of an instron-type tensile tester, in an environment of 25°C, the test piece was pulled at a peel rate of 300 mm/minute, and T-type peel strength (N/15 mm) between
PET/VMCPP was measured. This test was carried out five times, and a mean value thereof was obtained. (Interface Condition of Laminate)
The deposition surface, serving as a base, of the laminate was visually observed from the
PET film side through the PET film, and the interface condition (the condition of the adhesive layer on the deposition surface) of the laminate was evaluated in accordance with the following standards.
Co C or o: Neither orange-peel-like patterns nor Bl speck patterns were present on the deposition surface, and the adhesive layer is uniform. triangle: Orange-peel-like patterns and/or small speck patterns were observed slightly on the deposition surface but they were at a level that did not cause a problem in use. x: A number of orange-peel-like patterns and/or small speck patterns were observed on the deposition surface. [Table 2]
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2 = QO - £ slg 18 |S IN =e oO wy ol = ololv|lolo gle 515] 5 E = 2 2 8 ole :
SINNER ASUS E |S |g |B |g |g |E=
Sissi S i S22 — SE 2B Elo BT
O|—=|n| S| = ol o =) il Sle o 2 5 5 308 =18 8| |E|&|8|&s|&l s&s ol mn] SSS 3 FF wl 8 @ 0 |B QL= | * St Gy Ge 4 “lalglalala | SITE 2 EY LE ol ol SE S| Ey CE) S| 8 © I fe = Q Q Q of) 215185151515) |a\5k k|98 855 5\5(2T 28 Bal sl El Bg 83 3 = 3 2 SIS 280 ElvolglalE 5lE SE 5 Eg <1 Fo oF —~| Q&S =o 5] BB ~ 5|E| @ unl C| wT a B|-
RN ME EL I soa T|.8 iO a onl Sl cpl El of § =| oo
SSS ALTE] ef A o < c c| en gy of 5 : 3 SISA Cl 5 2 EA =19| #5] °|E&| of.§| of&| o 498888 | 15253 5430 ash £E 82 52 8 El sl E 8 8 <) wll 815215 5 18% E28 ls <8 gl 8s oN NN Ho = = g I bt ot =| i
SICIEl A&A [Ela eo E 2 8 gm < al gle ol | E g 8 8 Ee — 5] & O18 5 = E 5 ZI Eg Eg 2 al 8 i» 8 8 f 8 of 2 £ a £88 & [5 | |& g Sg 238% |% |% |¥ [© . Q
Ss |lolalalslalels # a | 2 |E|¥48 38 218 2 oF g Isl TiTeel gE 5 gd B13 [>]|° 8° S|° 5]|=® < 8 ~ DS ° |S © 3 dl & = <<] |<] |<] & = = = | ml X =| x px 2x Sg : g El = 8 Blo "jo Tu Yo Vs :
Q | 0 o 0 o a : 2 o 8 9 nn in nn = i
A ° = = a a a Q 2 2 = : g 2 © Q }NSal uopen[eA? = ¢ * E
EEE Z22-
From Table 2, it is understood that the condition of the adhesive layer on the deposition surface was excellent in Examples 1-11, which also exceled in the bonding strength. In particular, Examples 1 and 2 could exhibit a sufficient bonding strength in a short aging duration even if the environmental humidity during aging was high. In the meantime, Comparative
Example 1, in which only a component derived from 4,4'-MDI was used as an isocyanate component, was heavily affected by the environmental humidity during aging, and when aging was carried out in an environment of 25°C and 80% RT, the condition of the adhesive layer on the deposition surface was considerably poor and the bonding strength was extremely low as well. In addition, it is understood that, in Comparative Example 2 in which only a component derived from 2,4'-MDI was used as the isocyanate component and in Comparative Example 3 in which only isophorone diisocyanate was used, the condition of the adhesive layer on the deposition surface was excellent but the bonding strength was considerably low. It is to be noted that, in the case of Comparative Example 3, the temperature at an initial instance of viscosity measurement was 25°C, and the temperature at the viscosity measurement, which was carried out 30 minutes after the mixing, was 50°C; thus, at a glance, it seems that the viscosity had decreased when 30 minutes had passed. In the case of an example or a comparative example in which 2,4'-MDI and 4,4'-MDI were used, the reason why the viscosity was greater even when 30 minutes had passed even when the temperature at the measurement differs is that the reaction with the polyol component (A) had progressed. In other words, isophorone diisocyanate is less reactive than 2,4'-MDI and 4,4'-MD], and its reaction with the polyol component (A) does not progress much in 30 minutes or so at 50°C; thus, an increase in the viscosity is hardly observed, and an apparent decrease in the viscosity due to an influence of a measurement temperature is observed. In addition, it is considered that the bonding strength is considerably low because the reaction does not progress much through low-temperature, short-duration aging (25°C x 1 day or 2 days).
In addition, it is understood that, in Comparative Example 4 in which the low-molecular weight diol (b2) or triol (b3) was not contained as the polyol component (B), the condition of the adhesive layer on the deposition surface was excellent but the bonding strength was considerably low. Furthermore, it is understood that, when only a low-molecular weight diol (b2) or triol (b3) was used as the polyol component (B) (Comparative Examples 5, 6, and 7) or when the polyester ; diol (b1)-4 with Mn of 4,000 was used as the polyester diol (bl) (Comparative Example 8), the condition of the adhesive layer on the deposition surface was poor and the bonding strength was considerably low.
eT 23-
It is to be noted that, in Comparative Example 7, the viscosity obtained immediately after mixing was not inferior to those of the examples. However, since the polyol component (B) was composed only of the low-molecular weight triol (b3), there were many reaction sites with the polyisocyanate component (A), and thus the viscosity increased considerably in a short period of time as a result.
This application claims the benefit of priority to Japanese Patent Application No. 2013- 9142 filed on January 22, 2013 and Japanese Patent Application No. 2013-247979 filed on
November 29, 2013, entire disclosures of which are incorporated herein.
Industrial Applicability
The adhesive composition according to the present invention is suitably used to bond various types of plastic films together and to bond a plastic film with a metallized film or a metal foil, and in particular is suitable as a lamination adhesive for forming a packaging material for food, medical products, cosmetics, and so on. In addition, although the adhesive composition is suitable for joining thin film-like films together, the adhesive composition according to the present invention can be suitably used to join films not only of various thicknesses but also of various shapes and forms. Furthermore, the adhesive composition according to the present invention can be suitably applied to a solventless type and can thus be widely applied to the all the types of solvent-free adhesives.

Claims (8)

  1. - 24- 7 CLAIMS i
    I. An adhesive composition comprising a polyisocyanate component (A) and a polyol - component (B), wherein = the polyisocyanate component (A) is a reaction product obtained by reacting isocyanate - essentially containing 2,4'-diphenylmethane diisocyanate (al) and 4,4'-diphenylmethane ~ diisocyanate (a2) with a polyol essentially containing a polyether polyol (a3) under a condition - of excessive isocyanate groups, and ~ the polyol component (B) is a polyol composition essentially containing a polyester diol - (bl) with a number-average molecular weight of 500 or more and 3,000 or less and further = containing at least one of a diol (b2) with a number-average molecular weight of 50 or more and o less than 500 and a triol (b3) with a number-average molecular weight of 50 or more and less oy than 500.
  2. 2. The adhesive composition according to Claim 1, wherein, based on a total of 100 mol% of 2,4'-diphenylmethane diisocyanate (al) and 4,4'-diphenylmethane diisocyanate (a2), 2,4-diphenylmethane diisocyanate (al) is 10 mol% or more and 60 mol% or less, and 4,4'- diphenylmethane diisocyanate (a2) is 40 mol% or more and 90 mol% or less.
  3. 3. The adhesive composition according to Claim 1, wherein, based on 100 mass%.-of the polyol component (B), the adhesive composition includes the polyester diol (bl) in 60 mass% or more and 99 mass% or less, and the diol (b2) and the triol (b3) in combination in 1 mass% or more and 40 mass% or less.
  4. 4. The adhesive composition according to Claim |, wherein, based on 100 moles of a : hydroxyl group in the polyol component (B), the number of moles of an isocyanate group in the polyisocyanate component (A) is 70 moles or more and 300 moles or less.
  5. 5. The adhesive composition according to Claims 1, wherein the adhesive composition is ofasolventless type. ;
  6. 6. The adhesive composition according to Claims 1, wherein the adhesive composition is a lamination adhesive for forming a packaging material.
  7. 7. A laminate formed by laminating at [east two sheet-like substrates by using the adhesive composition according to any one of Claims 1-6.
  8. 8. A method for manufacturing a laminate, comprising: ) applying an adhesive composition according to any one of Claims 1-6 on a first sheet-like ] substrate to form an adhesive layer; overlaying the adhesive layer with a second sheet-like substrate; and po curing the adhesive layer interposed between the two sheet-like substrates. - -
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Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6361494B2 (en) * 2014-12-19 2018-07-25 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 laminate
JP5812219B1 (en) * 2015-04-17 2015-11-11 東洋インキＳｃホールディングス株式会社 Adhesive composition and laminate using the same
JP5975189B1 (en) * 2016-02-01 2016-08-23 東洋インキＳｃホールディングス株式会社 Laminated body and manufacturing method thereof
JP6090522B1 (en) * 2016-03-29 2017-03-08 東洋インキＳｃホールディングス株式会社 Laminated body and manufacturing method thereof
JP6747900B2 (en) * 2016-07-26 2020-08-26 Ｄｉｃグラフィックス株式会社 High solid adhesive composition
JP6664845B2 (en) * 2016-08-09 2020-03-13 東洋インキＳｃホールディングス株式会社 Laminate and manufacturing method thereof
JP6664846B2 (en) * 2016-08-19 2020-03-13 東洋インキＳｃホールディングス株式会社 Laminate and manufacturing method thereof
EP3549994A4 (en) * 2016-11-30 2020-08-05 Nitto Denko Corporation Adhesive composition, adhesive layer, and adhesive sheet
WO2018101372A1 (en) * 2016-11-30 2018-06-07 日東電工株式会社 Adhesive composition, adhesive layer, and adhesive sheet
JP6323580B1 (en) * 2017-02-14 2018-05-16 東洋インキＳｃホールディングス株式会社 Adhesive and adhesive sheet
JP6911445B2 (en) * 2017-03-27 2021-07-28 東洋インキＳｃホールディングス株式会社 Laminated body and its manufacturing method
WO2019116905A1 (en) * 2017-12-13 2019-06-20 Dic株式会社 Reactive adhesive, laminated film, and packaging body
JP2020026105A (en) * 2018-08-14 2020-02-20 凸版印刷株式会社 Gas barrier laminate
US11072725B2 (en) 2018-12-19 2021-07-27 Crosslink Technology, Inc. Polyurethane compositions for coating
JP2021098825A (en) * 2019-12-23 2021-07-01 東洋インキＳｃホールディングス株式会社 Solvent-free adhesive and laminate
WO2022220151A1 (en) * 2021-04-13 2022-10-20 Dic株式会社 Two-pack curable adhesive composition, anchor coating material, adhesive, laminate, and packaging material
WO2023032690A1 (en) 2021-08-31 2023-03-09 Dic株式会社 Adhesive, laminate, method for manufacturing laminate, and packaging material
JP2023148008A (en) * 2022-03-30 2023-10-13 東洋インキＳｃホールディングス株式会社 Solvent-free adhesives, laminates and packaging
JP7552962B1 (en) * 2022-12-21 2024-09-18 東ソー株式会社 Coating film, molded body, and coating agent containing polyurethane resin
WO2024252934A1 (en) 2023-06-08 2024-12-12 Dic株式会社 Polyisocyanate composition, two-part curable composition, two-part curable adhesive, laminate, and packaging material

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63196678A (en) * 1987-02-09 1988-08-15 Dainippon Ink & Chem Inc Adhesive composition for laminate film
JP2619434B2 (en) * 1987-11-18 1997-06-11 サンスター技研株式会社 Thixotropic stable one-pack moisture-curable polyurethane resin composition
US6136136A (en) * 1992-11-25 2000-10-24 Henkel Corporation Moisture-curable polyurethane hotmelt adhesives with high green strength
PT797604E (en) * 1994-05-25 2000-05-31 Henkel Kgaa POLYURETHANE FUSING TAIL THAT STRESSES THROUGH HUMIDITY ACTION
JPH10102031A (en) * 1996-09-30 1998-04-21 Dainippon Ink & Chem Inc Production of polyurethane resin for adhesive
US6884904B2 (en) * 2001-04-12 2005-04-26 Air Products And Chemicals, Inc. MDI-based polyurethane prepolymer with low monomeric MDI content
JP4074910B2 (en) * 2001-10-26 2008-04-16 大日本インキ化学工業株式会社 Floor construction method
US20030206775A1 (en) * 2002-05-03 2003-11-06 Markusch Peter H. Polyurethane/geotextile composite liner for canals and ditches based on liquefied monomeric MDI-derivatives
US6706776B2 (en) * 2002-06-18 2004-03-16 Bayer Corporation Syntactic foams with improved water resistance, long pot life and short demolding times
JP5604407B2 (en) * 2010-12-21 2014-10-08 ローム アンド ハース カンパニー Adhesive composition

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