CN110894418A - Two-component adhesive, laminate, and packaging material - Google Patents

Two-component adhesive, laminate, and packaging material Download PDF

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Publication number
CN110894418A
CN110894418A CN201910870025.XA CN201910870025A CN110894418A CN 110894418 A CN110894418 A CN 110894418A CN 201910870025 A CN201910870025 A CN 201910870025A CN 110894418 A CN110894418 A CN 110894418A
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China
Prior art keywords
adhesive
film
component
polyol
isocyanate
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CN201910870025.XA
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Chinese (zh)
Inventor
梅津清和
德永千勇
田边英男
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DIC Corp
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DIC Corp
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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
    • 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
    • B32B15/08—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 of synthetic resin
    • B32B15/088—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 of synthetic resin comprising polyamides
    • 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
    • B32B15/08—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 of synthetic resin
    • B32B15/09—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 of synthetic resin comprising polyesters
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/08—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 of synthetic resin
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • C08G18/70—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
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

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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)
  • Wrappers (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides: a two-component type adhesive having: a polyol component A containing a polyol compound and an isocyanate component B containing an isocyanate compound, wherein the isocyanate component B contains polymethylene polyphenylene isocyanate and at least one diphenylmethane diisocyanate monomer selected from the group consisting of 4, 4 ' -diphenylmethane diisocyanate, 2, 4 ' -diphenylmethane diisocyanate and 2, 2 ' -diphenylmethane diisocyanate, and has an isocyanate group content of less than 33 mass%; a laminate obtained by laminating a plurality of films or papers with an adhesive, wherein the adhesive is the above-mentioned two-component adhesive; and a packaging material.

Description

Two-component adhesive, laminate, and packaging material
Technical Field
The present invention relates to a two-component adhesive, and a laminate and a packaging material using the same.
Background
Laminated films (also referred to as laminated films) used for various packaging materials, labels, and the like are provided with design properties, functionality, storage properties, convenience, and transportability by laminating various plastic films, metal foils, papers, and the like, and particularly, a package formed by forming the laminated film into a bag shape is used as a package for foods, pharmaceuticals, lotions, and the like.
Conventionally, a main stream of laminated films is a laminated film obtained by a dry lamination method in which an adhesive dissolved in a volatile organic solvent (sometimes referred to as a solvent-based laminating adhesive) is applied to a film, the organic solvent is volatilized during passage through an oven, and another film is laminated, but in recent years, from the viewpoint of reducing environmental load and improving working environment, there has been an increasing demand for a reactive two-component type laminating adhesive (sometimes referred to as a two-component type adhesive or a solvent-free laminating adhesive) containing no volatile organic solvent (for example, see patent document 1).
The two-component adhesive described in patent document 1 is effective in terms of the adhesive strength and the short curing time of the solvent-free adhesive, but is a resin having a short pot life as a resin for the solvent-free adhesive because it combines an aromatic isocyanate as a curing agent and a polyester diol as a main agent. When the pot life is short, variation in the amount of coating is likely to occur, and as a result, the laminate appearance may be significantly impaired, and when the laminating apparatus is temporarily stopped, such as when a material is replaced, operations such as replacement of an adhesive and cleaning of a roller are required, and workability may also be significantly impaired. In particular, when 4, 4' -diphenylmethane diisocyanate (MDI), which is one of aromatic isocyanates, is used as the curing agent, the compound has high crystallinity, and thus the curing agent itself may be crystallized and precipitated.
Further, the two-component adhesive uses a reactive monomer having a slightly lower molecular weight than the solvent-based pressure-sensitive adhesive as a raw material, and therefore may be eluted into the contents through the laminated film. In particular, in recent years, control of ingredients eluted (transferred) from a plastic container by a chemical substance is defined in detail, including europe, and products with less eluted ingredients of a chemical substance from a container are demanded. Generally, sml (specific migration limit) is defined for elution of chemical substances used for adhesives, and the eluted substances can be easily controlled, but there are the following problems: it is not possible to easily remove the elution of an unintended additive substance (NIAS) generated during synthesis or the like.
On the other hand, an adhesive comprising an isocyanate-terminated polyurethane prepolymer which is a reaction product with a modified diphenylmethane diisocyanate (MDI) selected from carbodiimide-modified diphenylmethane diisocyanate, allophanate-modified diphenylmethane diisocyanate, biuret-modified diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, and combinations thereof, and a polyol is known as an adhesive that generates a low concentration of extractable Primary Aromatic Amine (PAA) (for example, see patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2014-159548
Patent document 2: japanese Kokai publication Hei-2014-516321
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a two-component adhesive that has excellent curing speed and, when used as a two-component adhesive, has very few unintended substances that elute into the contents through the laminated film.
Means for solving the problems
The inventors of the present invention found that: the above problems can be solved by a two-component adhesive using only crude MDI as an isocyanate component.
That is, the present invention provides a two-component adhesive having: a polyol component A containing a polyol compound and an isocyanate component B containing an isocyanate compound,
the isocyanate component B contains polymethylene polyphenylene isocyanate (ポリメチレンポリフェニレンイソシア - ト) and at least one diphenylmethane diisocyanate monomer selected from the group consisting of 4, 4 ' -diphenylmethane diisocyanate, 2, 4 ' -diphenylmethane diisocyanate and 2, 2 ' -diphenylmethane diisocyanate, and has an isocyanate group content of less than 33% by mass.
The present invention also provides a laminate obtained by laminating a plurality of films or papers with an adhesive, wherein the adhesive is the above-mentioned two-component adhesive.
The present invention also provides a laminate obtained by laminating a film or paper provided with a plurality of print layers with an adhesive, wherein the adhesive is the above-mentioned two-component adhesive.
The present invention also provides a packaging material produced by molding the laminate into a bag shape.
ADVANTAGEOUS EFFECTS OF INVENTION
The two-component adhesive of the present invention has an excellent curing rate and very little unintended substances eluted into the contents through the laminated film, and therefore, when the contents such as a detergent or a chemical are filled or after a certain period of time has elapsed since the contents are filled, the laminated structure is not peeled off, and a laminated body having excellent adhesiveness and content resistance can be obtained.
Detailed Description
(definition of wording solvent)
The two-component adhesive of the present invention is a reactive two-component type laminating adhesive as described above, and is also called a solvent-free two-component adhesive or a solvent-free laminating adhesive because conventional volatile organic solvents are not used.
In the present invention, an adhesive that is cured by a chemical reaction between an isocyanate group and a hydroxyl group is used. The "solvent" of the solventless adhesive according to the present invention means: the "solvent-free" means that the organic solvent having high solubility and high volatility is not contained, and the organic solvent having high solubility can dissolve the polyisocyanate and the polyol used in the present invention. Specific examples of the highly soluble organic solvent include toluene (トルエン), xylene (キシレン), methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, Methyl Ethyl Ketone (MEK), cyclohexanone, toluene (トルオ - ル), xylene (キシロ - ル), n-hexane, and cyclohexane. Among them, toluene, xylene, dichloromethane, tetrahydrofuran, methyl acetate, and ethyl acetate are known as organic solvents having particularly high solubility.
On the other hand, when there is a demand for low viscosity or the like, the adhesive of the present invention can be diluted with the above-mentioned organic solvent having high solubility as appropriate depending on the desired viscosity and used. In this case, either the polyol 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, and cyclohexane. Among these, ethyl acetate and Methyl Ethyl Ketone (MEK) are preferable, and ethyl acetate is particularly preferable, from the viewpoint of solubility. The amount of the organic solvent used varies depending on the viscosity required, and is usually in the range of about 0.1 to 10% by mass.
In order to reduce the viscosity of the adhesive of the present invention, a solvent having no hydroxyl group but having a carbonyl group and a boiling point of 200 ℃ or higher, such as triacetin or propylene carbonate, may be used. The amount of the organic solvent having a high boiling point is usually 0.1 to 10% by mass, depending on the viscosity and the physical properties of the coating film.
(definition of terms host agent and curing agent)
In general, in the two-component type adhesive, various adhesives exist in the expression "two components", but in the present invention, the isocyanate component B containing an isocyanate compound is referred to as "curing agent", and the polyol component a containing a polyol compound is referred to as "main agent".
(polyol component A containing a polyol compound as a main component)
In the present invention, the polyol compound contained in the polyol component a as the main component is not particularly limited, and known polyols can be used. There may be mentioned, for example, polymer polyols selected from polyester polyols, polyether polyols, polyurethane polyols, polyester polyether polyols, polyester (polyurethane) polyols, polyether (polyurethane) polyols, polyesteramide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyalkanes, castor oil or mixtures thereof; castor oil polyols such as polyether castor oil polyols and polyester castor oil polyols obtained by reacting various polyols with a polymer polyol selected from castor oil or a mixture thereof.
Examples of the polyester polyol include polyester polyols obtained by reacting a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, or a dialkyl ester thereof, or a mixture thereof with a diol such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, neopentyl glycol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 3' -dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, or a mixture thereof, or polyester polyols obtained by ring-opening polymerization of a lactone such as polycaprolactone, polypentanolide, or poly (β -methyl- γ -valerolactone).
Examples of the polyether polyol include polyether polyols obtained by polymerizing ethylene oxide compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using a low-molecular-weight polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as an initiator. Examples of the polyether polyol include polyether polyols obtained by reacting a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, a dialkyl ester thereof, or a mixture thereof with the polyether polyol.
The polyurethane polyol is a polyol having a urethane bond in 1 molecule, and includes, for example, a reaction product of a polyether polyol having a number average molecular weight of 200 to 20000 and an organic polyisocyanate, and NCO/OH is preferably less than 1, more preferably 0.9 or less. As the organic polyisocyanate, a polyisocyanate compound, particularly a diisocyanate compound, described later can be used.
Examples of the polyether (polyurethane) polyol and the polyester (polyurethane) polyol include reaction products of polyester polyol, polyetherester polyol and the like with organic polyisocyanate, and NCO/OH is preferably less than 1, more preferably 0.9 or less.
The polyesteramide polyol can be obtained by using, as a raw material, an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine, or the like in the esterification reaction.
Examples of the acrylic polyol include those obtained by copolymerizing hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or the like containing 1 or more hydroxyl groups in 1 molecule, or methacrylic acid derivatives corresponding thereto, with, for example, acrylic acid, methacrylic acid, or esters thereof.
Examples of the polycarbonate polyol include those obtained by the reaction of 1 or 2 or more kinds of diols selected from ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 1, 9-nonanediol, 1, 8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, bisphenol a, and hydrogenated bisphenol a, with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, and the like.
Examples of the polyhydroxyalkane include butadiene and a liquid rubber obtained by copolymerizing butadiene with acrylamide or the like.
As the polyol compound used in the present invention, a polyol compound having a urea bond group at the terminal, which is a reactant of polyisocyanate and bis (hydroxyalkyl) amine, can also be preferably used.
The number average molecular weight of the polyol component a is not particularly limited, and is usually adjusted to a range of 500 to 3000 in many cases from the viewpoint of an appropriate resin viscosity at the time of coating.
In the present invention, the number average molecular weight (Mn) is a value measured by Gel Permeation Chromatography (GPC) under the following conditions.
A measuring device: HLC-8220GPC, manufactured by Tosoh corporation
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh corporation and TSK-GELSuperHZM-Mx 4 manufactured by Tosoh corporation
A detector: RI (differential refractometer)
Data processing: multi Station GPC-8020model II from 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 was filtered through a microfilter at a concentration of 0.2 mass% in terms of solid content of the resin (100. mu.l)
The acid value of the polyol compound contained in the polyol component A is preferably not more than 10mgKOH/g, more preferably not more than 5 mgKOH/g. The lower limit is not less than 0 mgKOH/g.
The hydroxyl value of the polyol compound contained in the polyol component A is preferably 50mgKOH/g or more.
Among them, the polyol compound contained in the polyol component a is preferably polyester polyol, polyester polyether polyol, or castor oil polyol.
(curing agent containing isocyanate Compound isocyanate component B)
In the present invention, as the isocyanate component B of the curing agent, an isocyanate component containing crude MDI, that is, at least one diphenylmethane diisocyanate monomer selected from the group consisting of 4, 4 ' -diphenylmethane diisocyanate, 2, 4 ' -diphenylmethane diisocyanate and 2, 2 ' -diphenylmethane diisocyanate, and polymethylene polyphenylene isocyanate, and having an isocyanate group content of less than 33 mass% is used. MDI is an abbreviation for diphenylmethane diisocyanate.
In the present invention, generally, as polymeric MDI (also referred to as crude MDI), commercially available products can be used. It should be noted that polymeric MDI (crude MDI) is a mixture of single MDI having various isomer contents and polynuclear bodies of several structures.
The isocyanate group content of the crude MDI was calculated as follows.
[ NCO (% by mass) ]
About 1g of the isocyanate component B was precisely weighed into a 200mL Erlenmeyer flask, 10mL of 0.5N di-N-butylamine (toluene solution), 10mL of toluene and an appropriate amount of bromophenol blue were added thereto, and then about 100mL of methanol was added thereto and dissolved. The mixture was titrated with 0.25N hydrochloric acid solution. The NCO (% by mass) was determined by the following equation.
[ mathematical formula 1]
NCO (mass%) (blank titration-0.5N hydrochloric acid solution titration) x 4.202 x 0.25N factor of hydrochloric acid solution x 0.25 ÷ sample weight
Commercially available crude MDI is available from Yantai Wanhua Co., BASF INOAC POLYURETHANE Co., Ltd., and examples thereof include Wannate PM-200 manufactured by Yantai Wanhua Co., Ltd., and LUPRANATE M20S manufactured by BASF INOAC POLYURETHANE Co., Ltd.
The polymethylene polyphenylene isocyanate contained in 100 mass% of the crude MDI used in the present invention is preferably 50 to 70 mass%. By setting the polymethylene polyphenylene isocyanate content within the above range, a laminate having a better appearance can be obtained when a film base material having a high gas barrier property is used and coating/bonding is performed at a high speed.
In the present invention, the isocyanate component B containing an isocyanate compound is preferably composed of only an isocyanate having a skeleton derived from diphenylmethane diisocyanate, and is preferably composed of only crude MDI. It is preferred that isocyanate compounds having other skeletons are not contained.
The mixing ratio of the polyol component A containing a polyol compound and the isocyanate component B containing an isocyanate compound is such that the equivalent ratio [ (a)/(B) ] of the hydroxyl equivalent weight as a solid content of the polyol compound (a) to the isocyanate equivalent weight as a solid content of the polyisocyanate compound (B) is 1.0 to 5.0, more preferably 2.0 to 3.0. Details of the manufacture are described in the examples.
(viscosity)
The two-component adhesive of the present invention preferably has a viscosity of 5000mPa · s or less after the polyol component a and the isocyanate component B are blended in a weight ratio and left to stand in an atmosphere at 40 ℃ for 30 minutes. In the present invention, the viscosity is a value measured by a rotational viscometer under the following conditions.
A measuring device: MCR-302 manufactured by Anton Paar
The measurement conditions were as follows: temperature 40 ℃ and cone plate phi 50mm
Among them, the viscosity is preferably in the range of 500 to 5000 mPas, more preferably in the range of 1500 to 4500 mPas.
As described above, the two-component adhesive of the present invention contains the polyol component a and the isocyanate component B as essential components, and further, the aliphatic cyclic amide compound is mixed into either one of the polyol component a and the isocyanate component B or blended as a third component at the time of coating, whereby elution of harmful low-molecular chemical substances such as aromatic amines into the contents in the laminated package can be effectively suppressed.
The aliphatic cyclic amide compounds used herein include, for example, δ -valerolactam, e-caprolactam, e-enantholactam, η -caprylolactam, β -propiolactam, and the like, among these, e-caprolactam is preferable from the viewpoint of excellent effect of reducing the elution amount of low-molecular chemical substances, and it is preferable to mix the aliphatic cyclic amide compounds in an amount of 0.1 to 5 parts by mass based on 100 parts by mass of the polyol component a.
The two-component adhesive of the present invention may be used in combination with pigments as required. The pigment to be used in this case is not particularly limited, and examples thereof include organic pigments such as a filler pigment, a white pigment, a black pigment, a gray pigment, a red pigment, a brown pigment, a green pigment, a blue pigment, a metal powder pigment, a luminescent pigment and a pearl pigment described in the 1970 edition of the paint materials (edited by the japan paint industries co., ltd.), inorganic pigments, 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, hansa yellow, and lake red 4R; soluble azo pigments such as lake red C, carmine 6B, and jujube 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 sky blue; various dye-building pigments such as anthraquinone pigments, thioindigo pigments, and perinone pigments (ぺリノン series); various quinacridone pigments such as CINQUASIARED 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, and molybdate orange; various ferrocyanides such as prussian blue; various metal oxides such as titanium oxide, zinc white, brown yellow (マピコエロ one), 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 iron oxide pigments coated with metal oxides, and pearl pigments; graphite, carbon black, and the like.
Examples of the extender pigment include sedimentary barium sulfate, chalk, sedimentary calcium carbonate, calcium hydrogen carbonate, calcite, alumina white, silica, hydrous micro-powder silica (white carbon), ultrafine anhydrous silica (AEROSIL), silica sand (silica sand), talc, sedimentary magnesium carbonate, bentonite, clay, kaolin, and loess.
Further, examples of the plastic pigment include "GRANDOLL PP-1000" and "PP-2000S" manufactured by DIC.
The pigment used in the present invention is more preferably an inorganic oxide such as titanium oxide or zinc white as a white pigment or carbon black as a black pigment, from the viewpoint of excellent durability, weather resistance and appearance.
The mass ratio of the pigment used in the present invention is preferably 1 to 400 parts by mass, more preferably 10 to 300 parts by mass, based on 100 parts by mass of the total of the isocyanate component B and the polyol component a, from the viewpoint of excellent adhesiveness, blocking resistance, and the like.
In addition, the two-component adhesive of the present invention may also use an adhesion promoter. 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 -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethyldimethoxysilane and N-phenyl- γ -aminopropyltrimethoxysilane, epoxysilanes such as β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ -glycidoxypropyltrimethoxysilane and γ -glycidoxypropyltriethoxysilane, vinylsilanes such as vinyltris (β -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and γ -methacryloxypropyltrimethoxysilane, hexamethyldisilazane and γ -mercaptopropyltrimethoxysilane.
Examples of the titanate-based coupling agent include titanium tetraisopropoxide, titanium tetra-n-butoxide, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctanediol titanate, titanium lactate, and titanium tetrastearoxide.
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 (ノボラツク type) epoxy resin, β -methylglycidyl ether of bisphenol, β -methylglycidyl ether of phenol resin (ノボラツク type resin), a cyclic ethylene oxide type epoxy resin, and a resorcinol type epoxy resin, which are generally commercially available.
The two-component adhesive used in the present invention may contain other additives than the above-mentioned additives, if necessary. Examples of the additive include leveling agents; 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; an enhancer; a plasticizer; a lubricant; a rust inhibitor; a fluorescent whitening agent; an inorganic heat ray absorber; a fire retardant; an antistatic agent; dehydrating agents and the like.
These pigments, adhesion promoters and additives may be mixed with either the isocyanate component B or the polyol component a or blended as the 3 rd component at the time of coating. Among these, from the viewpoint of workability, it is preferable to adjust a premix obtained by blending a pigment, an adhesion promoter and an additive in advance into the polyol component a to obtain the polyol composition for a laminating adhesive of the present invention, and use the composition as a two-component adhesive.
(laminated body)
The laminate of the present invention is obtained by, for example, laminating a plurality of films or papers by a solventless lamination method using the adhesive of the present invention.
The film to be used is not particularly limited, and a film suitable for the purpose may be appropriately selected. Examples of the food packaging applications include polyolefin films such as polyethylene terephthalate (PET) films, polystyrene films, polyamide films, polyacrylonitrile films, polyethylene films (LLDPE: low density polyethylene films and HDPE: high density polyethylene films), polypropylene films (CPP: unstretched polypropylene films and OPP: biaxially stretched polypropylene films); plastic films (also referred to as polymer films) such as polyvinyl alcohol films and ethylene-vinyl alcohol copolymer films.
The film may be a film subjected to a stretching treatment. As a stretching treatment method, generally, a resin is melt-extruded by an extrusion film-forming method or the like to be formed into a sheet, and then simultaneously biaxially stretched or sequentially biaxially stretched. In the case of sequential biaxial stretching, generally, the longitudinal stretching treatment is performed first, and then the transverse stretching is performed. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.
Alternatively, a film in which a vapor deposition layer of a metal such as aluminum, a metal oxide such as silica or alumina, or a barrier film containing a gas barrier layer of polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, vinylidene chloride, or the like is laminated may be used in combination. By using such a film, a laminate having barrier properties against water vapor, oxygen, alcohol, inert gas, volatile organic compounds (aroma), and the like can be produced.
The film surface may be subjected to various surface treatments such as flame treatment, corona discharge treatment, etc. as necessary to form an adhesive layer free from defects such as film cracking, dishing, etc.
Alternatively, the laminate of the present invention can be obtained by coating the adhesive of the present invention as an adhesive auxiliary agent (anchor coating agent) on a film using a laminator, curing the adhesive, and then laminating the melted polymer material using an extruder (extrusion lamination method). As the film, the same film as that used in the above-described dry lamination method or solvent-free lamination method can be used. The polymer material to be melted is preferably a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin.
More specific examples of the laminate include:
(1) substrate film 1/adhesive layer 1/sealing film
(2) Substrate film 1/adhesive layer 1/metal vapor deposition unstretched film
(3) Substrate film 1/adhesive layer 1/metal vapor-deposited stretched film
(4) Transparent evaporation stretched film/adhesive layer 1/sealing film
(5) Substrate film 1/adhesive layer 1/substrate film 2/adhesive layer 2/sealing film
(6) Substrate film 1/adhesive layer 1/Metal vapor deposition stretched film/adhesive layer 2/sealing film
(7) Substrate film 1/adhesive layer 1/transparent vapor-deposited stretched film/adhesive layer 2/sealing film
(8) Substrate film 1/adhesive layer 1/metal layer/adhesive layer 2/sealing film
(9) Substrate film 1/adhesive layer 1/substrate film 2/adhesive layer 2/metal layer/adhesive layer 3/sealing film
(10) Substrate film 1/adhesive layer 1/metal layer/adhesive layer 2/substrate film 2/adhesive layer 3/sealing film, and the like, but is not limited thereto.
Examples of the base film 1 used in the structure (1) include an OPP film, a PET film, and a nylon film. As the substrate film 1, a substrate film coated for the purpose of improving gas barrier properties, ink compatibility when a printing layer described later is provided, or the like can be used. Commercially available base film 1 to which coating is applied includes a K-OPP film, a K-PET film, and the like. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of the sealing film include a CPP film and an LLDPE film. The printing layer may be provided on the surface of the substrate film 1 on the adhesive layer 1 side (when a coated substrate film is used as the substrate film 1, the surface of the coating layer on the adhesive layer 1 side). The printing layer can be formed by a general printing method conventionally used for printing on a polymer film, using various printing inks such as gravure ink, flexo ink, offset ink, stencil ink, and inkjet ink.
Examples of the base film 1 used in the structures (2) and (3) include an OPP film and a PET film. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. As the metal deposition unstretched film, a VM-CPP film in which a metal such as aluminum is deposited on a CPP film may be used, and as the metal deposition stretched film, a VM-OPP film in which a metal such as aluminum is deposited on an OPP film may be used. In the same manner as in the configuration (1), a printed layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1.
Examples of the transparent vapor-deposited stretched film used in the configuration (4) include films obtained by vapor deposition of silica or alumina on an OPP film, a PET film, a nylon film, or the like. For the purpose of protecting an inorganic deposition layer of silica or alumina, a film coated on the deposition layer may be used. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. The sealing film may be the same as that of the composition (1). The printing layer may be provided on the surface of the transparent vapor-deposited stretched film on the side of the adhesive layer 1 (in the case of using a film coated on the inorganic vapor-deposited layer, the surface of the coating layer on the side of the adhesive layer 1). The method of forming the printed layer is the same as in the configuration (1).
Examples of the base film 1 used in the structure (5) include a PET film. The base film 2 may be a nylon film. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention. The sealing film may be the same as that of the composition (1). A printed layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1 in the same manner as in the configuration (1).
The substrate film 1 of the composition (6) may be the same as those of the compositions (2) and (3). Examples of the metal vapor-deposited stretched film include a VM-OPP film and a VM-PET film in which an OPP film and a PET film are subjected to metal vapor deposition such as aluminum. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention. The sealing film may be the same as that of the composition (1). A printed layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1, in the same manner as in the configuration (1).
The substrate film 1 constituting (7) may be a PET film. The transparent vapor-deposited stretched film may be the same as that of the composition (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. The sealing film may be the same as that of the composition (1). A printed layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1, in the same manner as in the configuration (1).
The substrate film 1 constituting (8) may be a PET film. Examples of the metal layer include aluminum foil. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. The sealing film may be the same as that of the composition (1). A printed layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1, in the same manner as in the configuration (1).
Examples of the base film 1 constituting the components (9) and (10) include a PET film. The base film 2 may be a nylon film. Examples of the metal layer include aluminum foil. At least one of the adhesive layers 1, 2, and 3 is a cured coating film of the adhesive of the present invention. The sealing film may be the same as that of the composition (1). A printed layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1, in the same manner as in the configuration (1).
When the laminate of the present invention contains at least one of a metal vapor-deposited film, a transparent vapor-deposited film, and a metal layer, the adhesive layer in contact with the metal vapor-deposited layer, the transparent vapor-deposited layer, and the metal layer is preferably a cured coating film of the adhesive of the present invention.
Since the two-component adhesive of the present invention is solvent-free, the adhesive of the present invention, which is previously heated to about 40 to 100 ℃, is applied to a film material to be a base material using a roll such as a gravure roll, and then another base material is immediately bonded to obtain a laminate of the present invention. It is preferable to perform a curing treatment after lamination. The curing temperature is preferably room temperature to 70 ℃, and the curing time is preferably 6 to 240 hours.
The viscosity of the mixture of the adhesive is preferably about 300 to 3000 mPas at 40 ℃, and the viscosity of the adhesive of the present invention is 5000 mPas or less after the mixture is mixed and left at 40 ℃ for 30 minutes, so that the adhesive can be applied without any problem. Furthermore, the amount of the coating may be preferably 0.5 to 5g/m2More preferably 0.5 to 3g/m2The use is right and left.
When the two-component adhesive used in the present invention is used, the adhesive is cured at normal temperature or under heating for 12 to 72 hours after lamination, and practical properties are exhibited.
When the adhesive of the present invention is used as an adhesion auxiliary agent, the adhesive auxiliary agent of the present invention is applied to a film material to be a base material using a roll such as a gravure roll, the organic solvent is volatilized by heating in an oven or the like, and the melted polymer materials are laminated by an extruder, thereby obtaining a laminate of the present invention.
The amount of the adhesive applied is appropriately adjusted. In the case of a solvent-free adhesive, the amount of the adhesive applied is, for example, 1g/m2Above and 10g/m2Below, preferably 1g/m2Above and 5g/m2The following.
When the adhesive of the present invention is used as an adhesive auxiliary agent, the amount of the adhesive is, for example, 0.03g/m2Above and 0.09g/m2The following (solid content).
The laminate of the present invention may further include another film or substrate in addition to the above-described configurations (1) to (10). As the other substrate, a porous substrate such as paper, wood, leather, or the like described later may be used in addition to the above stretched film, unstretched film, and transparent vapor deposited film. The adhesive used for bonding another substrate may or may not be the adhesive of the present invention.
As the paper, a known paper base can be used without particular limitation. Specifically, natural fibers for papermaking such as wood pulp are used and produced by a known papermaking machine, and the papermaking conditions are not particularly limited. Examples of the natural fibers for papermaking include wood pulp such as softwood pulp and hardwood pulp, nonwood pulp such as manila pulp, sisal pulp and flax pulp, and pulp obtained by chemically modifying these pulps. As the kind of pulp, chemical pulp, ground pulp, chemically ground pulp, thermomechanical pulp, and the like based on a sulfate digestion method, an acid/neutral/alkaline sulfite digestion method, a sodium salt digestion method, and the like can be used.
Further, various commercially available high-quality papers, coated papers, linered papers, impregnated papers, yellow papers, and cardboard can be used. Further, a printed layer may be provided on the outer surface or inner surface of the paper layer as necessary.
The "other layer" may contain known additives, stabilizers, such as antistatic agents, easy-adhesion coating agents, plasticizers, lubricants, antioxidants, and the like. The "other layer" may be a layer obtained by subjecting the film surface to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, or the like as a pretreatment for improving adhesion when the film is laminated with another material.
As described above, in order to maximize the effect of the present invention that a laminate having high adhesiveness and excellent appearance after lamination processing can be obtained even under high-speed coating conditions, the adhesive of the present invention is preferably applied to a plastic film at first, and then the adhesive surface is bonded to another plastic film or a porous substrate other than plastic films, for example, a transparent vapor-deposited film, paper, wood, leather, or the like, to obtain a laminate.
The laminate of the present invention can be suitably used for various applications, for example, as packaging materials for foods, pharmaceuticals, living goods, lid materials, paper tableware such as paper straws, paper towels, paper spoons, paper dishes, and paper cups, firewall materials (wall-protecting materials), roof materials, solar cell panel materials, battery packaging materials, window materials, outdoor flooring materials, illumination protection materials, exterior sheets for use in outdoor industrial applications such as automobile parts, signboards, and stickers, decorative sheets for use in injection molding and simultaneous decoration methods, washing liquid lotions, kitchen liquid lotions, bath liquid soaps, liquid shampoos, liquid conditioners, and the like.
< packaging Material >
The laminate of the present invention is useful as a multilayer packaging material for the purpose of protecting foods, pharmaceuticals, and the like. When used as a multilayer packaging material, the layer structure thereof may be changed depending on the contents, the use environment, and the use form. Further, the package of the present invention may be provided with an easy-opening treatment and resealability means as appropriate.
The packaging material of the present invention is obtained by using the laminate of the present invention, stacking the sealing films of the laminate so that their surfaces face each other, and heat-sealing the peripheral ends thereof to form a bag. Examples of the bag-making method include: the laminate of the present invention is folded or stacked so that the inner layers (the sealing film surfaces) face each other, and the peripheral end portions thereof are heat sealed in a form such as a side seal type, a both side seal type, a three side seal type, a four side seal type, an envelope seal type, a seal with a seal palm, a seal with a pleat, a seal with a flat bottom, a seal with a square bottom, a square shape, or another heat seal type. The packaging material of the present invention can take various forms depending on the contents, the environment of use, and the form of use. A self-supporting packaging material (standing pouch) or the like may be used. The heat sealing method may be performed by a known method such as a bar seal, a rotary roll seal, a tape seal, a pulse seal, a high-frequency seal, or an ultrasonic seal.
The packaging material of the present invention is filled with contents through the opening thereof, and then the opening is heat-sealed to produce a product using the packaging material of the present invention. Examples of the contents to be filled include foods such as rice cakes, bean cakes, nuts, biscuits/cookies, wafer cakes, marshmallows, pies, semi-uncooked western cakes, candies, and snack foods; essential foodstuff such as bread, crisp noodles, instant noodles, dry noodles, pasta, aseptically packaged rice, vegetable porridge, packaged rice cake, cereal food, etc.; processed agricultural products such as pickles, boiled beans, natto, miso, frozen bean curd, mushroom, konjac, processed wild vegetables, jam, peanut butter, salad, frozen vegetables, and processed potato; processed livestock products such as ham, bacon, sausage, chicken processed product, beef canned food, fish ham/sausage, aquatic product processed product, fish cake, thallus Porphyrae, salty sea fish, dried bonito, salty fish meat, smoked salmon, and mustard radix Pseudostellariae; peach, orange, pineapple, apple, pear, cherry and other fruit pulps; vegetables such as corn, asparagus, mushroom, onion, carrot, radish, potato, etc.; cooked food such as frozen non-staple food and refrigerated non-staple food represented by hamburger, meatball, aquatic fried food, dumpling, and fried meat cake; dairy products such as butter, margarine, cheese, cream, instant cream powder, and formula milk powder for infant care; liquid flavoring agent, steamed curry, and pet food.
Further, it is also useful as various packaging materials for non-food products such as cigarettes, medical products such as disposable pocket warmers and infusion packs, liquid detergents for washing, liquid detergents for kitchens, liquid detergents for baths, liquid soaps for baths, liquid shampoos, liquid hair conditioners, cosmetics such as lotions and emulsions, vacuum insulation materials, batteries, and the like.
The packaging material of the present invention is particularly suitable for food and pharmaceutical applications where elution is a problem because the two-component adhesive is used.
Examples
The present invention will be specifically described below 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 ]
119 parts by mass of ethylene glycol and 290 parts by mass of diethylene glycol were put into a reaction vessel, and heated to 80 ℃ while stirring under a nitrogen gas stream. Further, 590 parts by mass of adipic acid was put into a reaction vessel while stirring, and heated to 150 to 240 ℃ to perform an esterification reaction. When the acid value is 5mgKOH/g or less, the reaction vessel is gradually depressurized, and the reaction is carried out at 200 to 240 ℃ for 3 hours under 1mmHg or less, whereby a polyester polyol resin having hydroxyl groups at both ends and an acid value of 2mgKOH/g and a molecular weight of about 1350 (hereinafter, this is abbreviated as "polyol component A1") is obtained.
Synthesis example 2[ Synthesis of polyol component A2 ]
129 parts by mass of ethylene glycol, 137 parts by mass of diethylene glycol, and 303 parts by mass of polypropylene glycol (having a molecular weight of about 1000, a diol) were charged into a reaction vessel, and the mixture was heated to 80 ℃ while stirring under a nitrogen stream. Then, 106 parts by mass of phthalic anhydride and 324 parts by mass of adipic acid were put into a reaction vessel while stirring, and heated to 150 to 220 ℃ to perform an esterification reaction. When the acid value reached 8mgKOH/g or less, the reaction vessel was gradually depressurized, and the reaction was carried out at 220 ℃ under 1mmHg or less for 3 hours to obtain a polyester polyether polyol resin having hydroxyl groups at both ends and an acid value of 3mgKOH/g and a molecular weight of about 1170 (hereinafter, this resin is abbreviated as "polyol component A2").
Synthesis example 3[ Synthesis of polyol component A3 ]
550 parts by mass of polypropylene glycol (having a molecular weight of about 3000 and a triol) and 450 parts by mass of castor oil (product name: KAKUKOUICHI I.W. oil Co., Ltd.) were charged into a reaction vessel, and the mixture was heated to 60 ℃ while stirring under a nitrogen gas stream to be uniformly dissolved. A polyether castor oil polyol resin having a hydroxyl value of 95mgKOH/g (hereinafter, this will be abbreviated as "polyol component A3") was obtained.
Comparative Synthesis example 1[ Synthesis of isocyanate component C1 as curing agent ]
A mixture of 4, 4 ' -diphenylmethane diisocyanate and 50/50 parts of 2, 4 ' -diphenylmethane diisocyanate (trade name: manufactured by LUPRANATE MI BIP Co.) 200 parts, 4 ' -diphenylmethane diisocyanate (trade name: manufactured by MILLIONATE MT-F Tosoh Co.) 339 parts, polypropylene glycol (molecular weight: about 1000)422 parts, and polypropylene glycol (molecular weight: about 400)39 parts were charged into a reaction vessel, and the reaction vessel was heated to 80 ℃ with stirring under a nitrogen gas stream to effect reaction, and when the reaction was completed, the reaction vessel was cooled to obtain an isocyanate component C1 having an isocyanate group concentration of about 13.6%.
(two-component adhesive examples and comparative examples)
The two-component adhesives of examples 1 to 6 and comparative example 1 were obtained according to the formulations shown in tables 1 and 2.
The crude MDI used was LUPRANATE M20S manufactured by BASF INOAC corporation, and the isocyanate group content was 31.2%.
(evaluation method)
[ evaluation of elution amount of harmful component (PAA) ]
The two-component adhesive obtained by combining the examples or comparative examples was applied in such an amount that the coating weight was adjusted toThe solid content was 3.0g/m2The right and left patterns were applied to a polyethylene terephthalate (referred to as PET) film, and the coated surface of the film was laminated to a linear low density polyethylene (referred to as LLDPE) film using a laminator to prepare a laminated film. The laminated film was stored in a thermostatic bath at 40 ℃ for 3 days.
120 mm. times.220 mm was cut from the laminate film, the resulting LLDPE film was bent so as to be the inner side, and the film was heat-sealed at 1atm and 180 ℃ for 1 second in 3 directions with a width of 10mm to prepare a content contact 2dm2The pouch of (1). The contents were added with a 3% acetic acid solution. The filled pouches were boiled for 98-1 hr to sterilize and then tested for extractable Primary Aromatic Amine (PAA) using LC/MS.
[ measurement of viscosity 40 to 30 minutes after compounding ]
The viscosity was measured with a rotational viscometer under the following conditions and was set to a value of mPa · s.
A measuring device: MCR-302 manufactured by Anton Paar
The measurement conditions were as follows: temperature 40 ℃ and cone plate phi 50mm
The viscosity was evaluated as follows.
Viscosity evaluation 1: 1000 to 3000 mPa.s
Viscosity evaluation 2: 3000 to 4000 mPa.s
Viscosity evaluation 3: 4000 to 5000mPa · s
Viscosity evaluation 4: 5000 mPa.s or more
[ lamination Strength ]
On the printing surface of a PET film on which a pattern was gravure-printed using UNIVURE NT (manufactured by DIC) as a printing ink, the amount of coating was 3.0g/m as a solid content2Two-component adhesives prepared by combining the examples and comparative examples were applied in the right and left directions. Thereafter, the adhesive-coated surface of the film was laminated to an LLDPE film by a laminator to prepare a laminated film. The laminated film was kept in a constant temperature bath at 40 ℃ for 3 days to prepare a laminated film for a lamination strength test.
A test piece was cut out from the laminated film at a width of 15mm, and the adhesive strength (N/15mm) was measured by T-peeling using a tensile tester at a peeling speed of 300 mm/min.
[ lamination Strength and appearance after boiling ]
On the printing surface of a PET film on which a pattern was gravure-printed with printing ink ("UNIVURE NT" manufactured by DIC corporation), the coating amount was 3.0g/m as a solid content2Two-component adhesives prepared by combining the examples and comparative examples were applied in the right and left directions. Thereafter, the coating surface of the film was laminated to an LLDPE film using a laminator to produce a laminated film. The laminated film was kept in a constant temperature bath at 40 ℃ for 3 days.
From this laminated film, 150mm × 300mm was cut, and the film was bent so that the LLDPE film was located inside, and heat-sealed at 1atm and 180 ℃ for 1 second to prepare a pouch. 1/1/1 flavoring sauce (meat flavoring sauce: vegetable oil: edible vinegar: 1) is added as the content.
The filled pouch is subjected to boiling sterilization treatment for 98-1 hr. The contents were removed, and a test piece was cut out from the laminated film at a width of 15mm, and the adhesive strength (N/15mm) was measured by T-peeling using a tensile tester at a peeling speed of 300 mm/min.
The appearance of each pouch after removal was observed, and whether or not delamination occurred was evaluated as follows.
Evaluation ○ No delamination
Evaluation △ delamination site 5 or less
Evaluation x: delamination site is more than 6
[ evaluation of curing Rate ]
The two-component adhesive obtained by combining the examples or comparative examples was applied in an amount such that the solid content was 3.0g/m2The left and right patterns were coated on plain nylon films. Thereafter, the adhesive-coated surface of the film was laminated to an LLDPE film by a laminator to prepare a laminated film.
The laminate film was stored in a thermostatic bath at 40 ℃, and the NCO reaction rate (%) was calculated from the absorbance of the NCO peak on day 1, day 2 and day 3 using an infrared spectrometer, and the curing rate was evaluated.
The curing speed was evaluated as follows.
Curing speed evaluation 1: NCO reaction rate of more than 90 percent
Curing speed evaluation 2: the NCO reaction rate is more than 70 percent and less than 90 percent
Evaluation of curing speed 3: the NCO reaction rate is more than 50 percent and less than 70 percent
Curing speed evaluation 4: NCO reaction rate is less than 50%
The evaluation results are shown in tables 1 and 2.
[ Table 1]
Figure BDA0002200789720000191
[ Table 2]
Figure BDA0002200789720000192
In the table, the abbreviations are as follows.
PPG 1000: EXCENOL 1020 manufactured by Asahi glass Inc
As a result, it was found that: the two-component adhesive of the present invention has an excellent curing rate and a very small amount of PAA elution.

Claims (5)

1. A two-component adhesive characterized by having: a polyol component A containing a polyol compound and an isocyanate component B containing an isocyanate compound,
the isocyanate component B contains polymethylene polyphenylene isocyanate and at least one diphenylmethane diisocyanate monomer selected from the group consisting of 4, 4 ' -diphenylmethane diisocyanate, 2, 4 ' -diphenylmethane diisocyanate and 2, 2 ' -diphenylmethane diisocyanate, and the isocyanate group content of the isocyanate component B is less than 33% by mass.
2. The two-pack adhesive according to claim 1, wherein the polyol compound contained in the polyol component A is a polyester polyol, a polyester polyether polyol or a castor oil polyol.
3. A laminate obtained by laminating a plurality of films or papers with an adhesive, wherein the adhesive is the two-component adhesive according to claim 1 or 2.
4. A laminate obtained by laminating a film or paper provided with a plurality of printed layers with an adhesive, wherein the adhesive is the two-component adhesive according to any one of claims 1 to 3.
5. A packaging material produced by forming the laminate according to claim 3 or 4 into a bag shape.
CN201910870025.XA 2018-09-13 2019-09-12 Two-component adhesive, laminate, and packaging material Pending CN110894418A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016175973A (en) * 2015-03-19 2016-10-06 Dic株式会社 Adhesive for lamination and laminated body using the same
JP2016204449A (en) * 2015-04-17 2016-12-08 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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02147685A (en) * 1988-11-30 1990-06-06 Yokohama Rubber Co Ltd:The Cold-setting polyurethane adhesive for wood
JP5719495B2 (en) * 2007-04-04 2015-05-20 オート化学工業株式会社 Two-component urethane-based curable composition, flooring adhesive and repair agent using the same, and flooring construction method and repairing method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016175973A (en) * 2015-03-19 2016-10-06 Dic株式会社 Adhesive for lamination and laminated body using the same
JP2016204449A (en) * 2015-04-17 2016-12-08 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

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