CN113710378A - Solution of hydroxyl-containing terminal urethane prepolymer and method for producing same, adhesive, and adhesive sheet and method for producing same - Google Patents

Solution of hydroxyl-containing terminal urethane prepolymer and method for producing same, adhesive, and adhesive sheet and method for producing same Download PDF

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Publication number
CN113710378A
CN113710378A CN202080029847.6A CN202080029847A CN113710378A CN 113710378 A CN113710378 A CN 113710378A CN 202080029847 A CN202080029847 A CN 202080029847A CN 113710378 A CN113710378 A CN 113710378A
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adhesive
hydroxyl
urethane prepolymer
active hydrogen
mass
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斋藤秀平
户根嘉孝
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Toyochem Co Ltd
Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/10—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an adhesive surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Abstract

The invention provides a solution of hydroxyl-containing terminal urethane prepolymer for adhesives, which has a reduced amount of organic solvent used, a relatively high solid content concentration, and a relatively low viscosity. And an adhesive which is reduced in the amount of the organic solvent used, has a relatively high solid content concentration, and has a relatively low viscosity at the time of application to provide good applicability to application. The solution of a hydroxyl-terminated urethane prepolymer for an adhesive of the present invention contains a hydroxyl-terminated Urethane Prepolymer (UPH) which is a reaction product of one or more active hydrogen group-containing compounds (HX) having a plurality of active hydrogen groups in one molecule and one or more polyisocyanates (N), and has a solid content concentration of 80 mass% or more and a viscosity of 8000 mPas or less at 25 ℃ after leaving at 25 ℃ for 1 hour immediately after production. The adhesive of the present invention comprises a solution of the hydroxyl group-containing terminal urethane prepolymer of the present invention and a polyfunctional isocyanate compound (I).

Description

Solution of hydroxyl-containing terminal urethane prepolymer and method for producing same, adhesive, and adhesive sheet and method for producing same
Technical Field
The present invention relates to a solution of a hydroxyl-containing terminal urethane prepolymer for an adhesive and a method for producing the same, an adhesive, and an adhesive sheet and a method for producing the same.
Background
Conventionally, as surface protection sheets for various members, adhesive sheets having an adhesive layer formed on a base sheet have been widely used. Examples of the adhesive include acrylic adhesives, silicone adhesives, and urethane adhesives. Acrylic adhesives have excellent adhesion, but have strong adhesion, and therefore have poor removability after being attached to an adherend. In particular, after a lapse of time under a high-temperature and high-humidity environment, the removability further decreases due to an increase in adhesive force, and there is a tendency that the adherend is easily contaminated by the adhesive remaining on the surface of the adherend after removability. Regarding the silicone adhesive, there are also the following concerns: the silicone resin having a relatively low molecular weight is likely to be adsorbed on the surface of a device such as an electronic component, causing a problem. In contrast, the urethane adhesive has good adhesion to an adherend, is excellent in removability, and is not easily volatile.
In the present specification, the "adhesive" is an adhesive having removability (removable adhesive), and the "adhesive sheet" is an adhesive sheet having removability (removable adhesive sheet).
Flat panel displays such as Liquid Crystal Displays (LCDs) and organic electroluminescent displays (OELDs), and touch panel displays in which the flat panel displays and a touch panel are combined are widely used in electronic devices such as Televisions (TVs), Personal Computers (PCs), mobile phones, and portable information terminals.
The urethane adhesive sheet can be preferably used as a surface protective sheet for flat panel displays, touch panel displays, and substrates produced or used in the production steps of these (glass substrates, ITO/glass substrates having an Indium Tin Oxide (ITO) film formed on a glass substrate, and the like), optical members, and the like.
The following methods are known as a method for producing a urethane adhesive: a method of using a hydroxyl-terminated urethane prepolymer which is a reaction product of an active hydrogen group-containing compound such as a polyol and a polyisocyanate, and a polyfunctional isocyanate compound; and a method of reacting a polyol with a polyfunctional isocyanate compound in one shot (one shot method) without using a hydroxyl-terminated urethane prepolymer.
A general method for producing an adhesive sheet includes: a coating step of coating an adhesive on a base sheet; a heating step of forming an adhesive layer containing a cured product of an adhesive by heating and drying the formed coating layer; a winding step of winding the obtained adhesive sheet around a core to form an adhesive sheet roll; and a curing step of curing the adhesive sheet roller.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5194801
Patent document 2: japanese patent No. 6270818
Patent document 3: japanese patent No. 5466366
Patent document 4: japanese patent No. 6070633
Disclosure of Invention
Problems to be solved by the invention
The urethane adhesive is cured immediately after production, but if the initial curing property is too high, there is a concern that: the pot life (pot life) becomes short, and the viscosity of the adhesive becomes too high to be uniformly applied until the adhesive is applied to the substrate sheet. If the initial curing property of the urethane adhesive is too low, there is a concern that: the coating layer or the adhesive layer is affected by hot air during heating and drying of the coating layer or by mechanical stress applied during winding and curing of the adhesive sheet obtained after heating and drying, and thus, a core step mark, an orange peel defect, a curl, and other surface appearance defects are generated in the adhesive layer. The urethane adhesive preferably has a good pot life and good initial curability.
In general, urethane adhesives have been adjusted to a relatively low viscosity suitable for application by containing an organic solvent. However, the use of Volatile Organic Compounds (VOC) is not preferable from the viewpoint of environmental aspects and the like, and the amount thereof is preferably small. With respect to a conventional urethane adhesive, when the amount of an organic solvent used is reduced, the viscosity of the adhesive increases, and the coatability tends to decrease.
It is preferable to provide a urethane adhesive having a relatively low viscosity suitable for application even when the amount of the organic solvent used is reduced to increase the solid content concentration. In general, the solid content concentration of the urethane adhesive is less than 70% by mass, but is preferably 70% by mass or more, and more preferably 80% by mass or more, from the viewpoint of VOC reduction.
Patent documents 1 to 4 are cited as related documents of the present invention.
Patent document 1 discloses a method for producing a urethane resin for adhesives, which comprises reacting a polyol with a polyisocyanate compound at an excess ratio of isocyanate groups to obtain an isocyanate group-terminated prepolymer, then reacting a chain extender with the isocyanate group-terminated prepolymer, and optionally reacting an end-stopper,
the chain extender comprises a polyfunctional compound (X) having three or more functional groups capable of reacting with an isocyanate group, two of the functional groups of the polyfunctional compound (X) being primary hydroxyl groups, the remaining functional groups being secondary or tertiary hydroxyl groups,
the polyfunctional compound (X) is at least one selected from the group consisting of the compound represented by the chemical formula (1) and the compound represented by the chemical formula (2) (first invention).
Patent document 1 discloses an adhesive containing a urethane resin obtained by the above production method (fifth invention).
Patent document 1 discloses a method for producing a solution of a hydroxyl-terminated urethane prepolymer by two-stage polymerization, and a urethane adhesive containing the solution of the hydroxyl-terminated urethane prepolymer.
Patent document 1 describes that "since the urethane resin is not gelled in the adhesive of the present invention, the solid content concentration may not be reduced in order to reduce the viscosity. "(paragraph 0055). However, the solid content concentration of the polyurethane solutions obtained in examples 1 to 8 was as low as 47 to 50 mass% (table 1), and the viscosity at 24 ℃ was as low as 3700 to 5100mPa · s (table 1), and it is estimated that the solid content concentration of the adhesive using the polyurethane solution was low, and the VOC reducing effect was not sufficient. That is, patent document 1 does not specifically describe a solution of a hydroxyl group-containing terminal urethane prepolymer having a high solid content concentration and an adhesive containing the same having a high solid content concentration.
Patent document 2 discloses a solvent-free type polyurethane adhesive which is prepared by mixing a polyurethane resin and a water-soluble solvent
(A) Average molecular weight 1.2X 104An active hydrogen compound having an average number of functional groups of 3,
(B) Average molecular weight of 0.1X 104An active hydrogen compound having an average number of functional groups of 2 or more, and
(C) an organic polyisocyanate having an average number of functional groups of 2 (first invention).
Patent document 2 describes that "the polyurethane-based adhesive of the present invention obtained by combining an active hydrogen compound (a) and an active hydrogen compound (B) is preferable in terms of a polymer having a moderate cohesive force and a soft structure. The polyurethane-based adhesive obtained in the above manner is advantageous in terms of applicability since the mixture has an appropriate viscosity at the time of application. "(paragraph 0019).
However, the urethane adhesive described in patent document 2 is a urethane adhesive obtained by a single-pass method. In general, an adhesive layer using a urethane adhesive obtained by a single process is hard, and the surface smoothness of the adhesive layer tends to be easily deteriorated by curing shrinkage. In particular, the urethane adhesive described in patent document 2 does not contain a diluent such as a solvent or a plasticizer, and therefore, the applicability is not said to be good, and the above tendency is remarkable. The viscosity of the urethane adhesive described in patent document 2 is not described in detail.
Patent document 3 discloses a one-pack solvent-free urethane adhesive composition containing: (A) a urethane prepolymer containing a terminal isocyanate group obtained by reacting a polyol with an excess amount of a polyisocyanate compound, (B) a fine powder-coated amine, and (C) an adhesion-imparting agent (first invention).
Patent document 3 describes "a solvent-free adhesive composition containing substantially no solvent. Therefore, when an adhesive body is produced from the adhesive composition of the present invention, environmental pollution due to odor, Volatile Organic Compounds (VOC), or the like can be prevented. "(paragraph 0025). However, the urethane adhesive described in patent document 3 does not contain a diluent such as a solvent or a plasticizer, and therefore, has poor coatability. The viscosity of the urethane adhesive described in patent document 3 is not described in detail.
Patent document 4 discloses a removable urethane adhesive composition containing: 100 parts by weight of a polyurethane resin (A) having a primary hydroxyl group at the end and a hydroxyl value of 10mgKOH/g to 40mgKOH/g, 1 part by weight to 20 parts by weight of a polyfunctional isocyanate compound (B), and 25 parts by weight to 100 parts by weight of at least one compound (C) selected from polyalkylene glycol compounds, epoxy compounds, and phosphate compounds (first invention).
In synthesis examples 1 to 5 and examples 1 to 18 of patent document 4, a polyurethane resin solution containing 60 mass% of nonvolatile components and a urethane adhesive containing the same were produced.
The solid content concentration of the polyurethane resin solutions obtained in synthesis examples 1 to 5 was a conventional general level, and the solid content concentration of the urethane adhesives described in examples 1 to 18 including the solid content was estimated to be a conventional general level, and the VOC reducing effect was insufficient and the viscosity was not detailed.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a solution of a hydroxyl group-containing terminal urethane prepolymer for an adhesive, which has a relatively low viscosity and a relatively high solid content concentration, and which is reduced in the amount of an organic solvent used.
Further, an object of the present invention is to provide an adhesive which has a small amount of an organic solvent used, a relatively high solid content concentration, and a relatively low viscosity at the time of application to provide good applicability to application.
Means for solving the problems
The solution of the hydroxyl-containing terminal urethane prepolymer for adhesives of the present invention comprises:
a hydroxyl-terminated Urethane Prepolymer (UPH) which is a reaction product of one or more active hydrogen group-containing compounds (HX) having a plurality of active hydrogen groups in one molecule and one or more polyisocyanates (N), and
the solid content concentration is 80 mass% or more, and the viscosity at 25 ℃ after standing at 25 ℃ for 1 hour immediately after the preparation is 8000 mPas or less.
In the solution of the hydroxyl group-containing terminal urethane prepolymer for adhesives of the invention,
the one or more active hydrogen group-containing compounds (HX) are preferably one or more polyols (HA) having a number average molecular weight of 1000 or more and one or more active hydrogen group-containing compounds (HB) having a number average molecular weight of less than 1000 and having a plurality of active hydrogen groups in one molecule.
The adhesive of the present invention comprises a solution of the hydroxyl group-containing terminal urethane prepolymer of the present invention and a polyfunctional isocyanate compound (I).
The adhesive of the present invention preferably has a solid content concentration of 80% by mass or more and a viscosity of 5000 mPas or less at 25 ℃ after leaving at 25 ℃ for 3 hours immediately after production.
The adhesive sheet of the present invention includes a substrate sheet and an adhesive layer containing a cured product of the adhesive of the present invention.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a solution of a hydroxyl group-containing terminal urethane prepolymer for an adhesive, which has a reduced amount of an organic solvent used, a relatively high solid content concentration, and a relatively low viscosity, can be provided.
Further, according to the present invention, it is possible to provide an adhesive which has a small amount of an organic solvent to be used, a relatively high solid content concentration, and a relatively low viscosity at the time of application to provide good applicability to application.
Drawings
FIG. 1 is a schematic cross-sectional view of an adhesive sheet according to a first embodiment of the present invention.
FIG. 2 is a schematic cross-sectional view of an adhesive sheet according to a second embodiment of the present invention.
Detailed Description
The solution of the hydroxyl-containing terminal urethane prepolymer for adhesives of the present invention comprises:
a hydroxyl-terminated Urethane Prepolymer (UPH) which is a reaction product of one or more active hydrogen group-containing compounds (HX) having a plurality of active hydrogen groups in one molecule and one or more polyisocyanates (N).
The adhesive of the present invention is a urethane-based adhesive comprising the solution of the hydroxyl group-containing terminal urethane prepolymer of the present invention and a polyfunctional isocyanate compound (I).
The adhesive sheet of the present invention is a urethane adhesive sheet comprising a substrate sheet and an adhesive layer containing a cured product of the adhesive of the present invention.
The solution of the hydroxyl-terminated urethane prepolymer for adhesives of the present invention has a reduced amount of organic solvent used, a relatively high solid content, and a relatively low viscosity. By using the solution of the hydroxyl group-containing terminal urethane prepolymer, the urethane adhesive of the present invention can be provided which has a reduced amount of organic solvent used, a relatively high solid content concentration, and a relatively low viscosity at the time of application to provide good applicability to application. The adhesive of the present invention is preferably used in a small amount of Volatile Organic Compounds (VOC) from the viewpoint of environmental aspects.
The solution of the hydroxyl-containing terminal urethane prepolymer for an adhesive of the present invention has a solid content concentration of 80% by mass or more and a viscosity at 25 ℃ of 8000 mPas or less after leaving at 25 ℃ for 1 hour immediately after the preparation.
The solid content concentration in the adhesive of the present invention is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The adhesive of the present invention has a viscosity at 25 ℃ of preferably 8000 mPas or less, more preferably 7000 mPas or less, and particularly preferably 5000 mPas or less after leaving to stand at 25 ℃ for 3 hours immediately after the preparation.
The preferred viscosity range varies depending on the coating method, but a low viscosity tends to result in excellent coatability. The adhesive of the present invention changes in viscosity with the passage of time immediately after preparation, "viscosity at 25 ℃ after standing at 25 ℃ for 3 hours immediately after preparation" is assumed to be "viscosity at the time of application".
In the present specification, unless otherwise specified, "solid content concentration" and "viscosity" are determined by the method described in [ example ].
[ Adhesives ]
(solution of hydroxyl-terminated urethane prepolymer)
The solution of the hydroxyl-terminated urethane prepolymer of the present invention is a solution containing a hydroxyl-terminated Urethane Prepolymer (UPH) obtained by copolymerizing one or more active hydrogen group-containing compounds (HX) having a plurality of active hydrogen groups in one molecule with one or more polyisocyanates (N). The copolymerization reaction may be carried out in the presence of one or more catalysts as required. If necessary, one or more solvents may be used in the copolymerization reaction.
In order to achieve a high solid content concentration and a low viscosity of the adhesive, the hydroxyl-terminated Urethane Prepolymer (UPH) is preferably a low molecular weight as compared with a conventional general hydroxyl-terminated urethane prepolymer. The weight average molecular weight (Mw) of the hydroxyl-terminated Urethane Prepolymer (UPH) is preferably 10000 to 100000, more preferably 13000 to 80000. Mw is preferably 60000 or less, more preferably 15000 to 60000, and particularly preferably 10000 to 60000.
In the present specification, "Mw" is a polystyrene-equivalent weight average molecular weight determined by Gel Permeation Chromatography (GPC) measurement. "Mn" is a number average molecular weight in terms of polystyrene determined by GPC measurement. These can be measured by the method described in [ example ].
The concentration of the solid content in the solution of the hydroxyl group-containing terminal urethane prepolymer of the present invention is 80 mass% or more, preferably 85 mass% or more, more preferably 90 mass% or more, and particularly preferably 95 mass% or more, from the viewpoint of VOC reduction of the adhesive.
From the viewpoint of pot life and coatability of the adhesive, the viscosity at 25 ℃ of the solution of the hydroxyl group-containing terminal urethane prepolymer of the present invention immediately after preparation and after standing at 25 ℃ for 1 hour is 8000mPa · s or less, preferably 7000mPa · s or less, more preferably 6000mPa · s or less, and particularly preferably 5000mPa · s or less.
In order to achieve a high solid content concentration and a low viscosity of the adhesive and to improve the initial hardenability of the adhesive, the one or more active hydrogen group-containing compounds (HX) that are raw materials of the hydroxyl-terminated Urethane Prepolymer (UPH) are preferably a compound (HB) containing one or more polyols (HA) (higher molecular weight component) having a number average molecular weight of 1000 or more and one or more active hydrogen groups (HB) (lower molecular weight component) having a number average molecular weight of less than 1000 and having a plurality of active hydrogen groups in one molecule.
That is, as the hydroxyl-terminal Urethane Prepolymer (UPH), a hydroxyl-terminal urethane prepolymer (UPH-S) which is a reaction product of one or more polyisocyanates (N) and a plurality of active hydrogen group-containing compounds (HX) containing one or more polyols (HA) having Mn of 1000 or more and one or more active hydrogen group-containing compounds (HB) having Mn less than 1000 are preferable.
From the viewpoint of pot life and initial hardenability, the one or more active hydrogen group-containing compounds (HX) that are raw materials of the hydroxyl-terminated Urethane Prepolymer (UPH) are preferably compounds containing an active hydrogen group that contains a primary hydroxyl group having moderate reactivity as an active hydrogen group. In particular, the at least one active hydrogen group-containing compound (HB) preferably contains a primary hydroxyl group having moderate reactivity as an active hydrogen group.
By adjusting the mass ratio of one or more polyols (HA) and one or more polyisocyanates (N) as higher molecular weight components, the weight average molecular weight (Mw) of the hydroxyl-terminated Urethane Prepolymer (UPH) can be made relatively small, and a high solid content concentration and a low viscosity of the adhesive can be achieved. In general, since a lower molecular weight hydroxyl-terminated Urethane Prepolymer (UPH) tends to have poor initial curability, the initial curability can be improved by using a lower molecular weight active hydrogen group-containing compound (HB) as one of the raw materials of the hydroxyl-terminated Urethane Prepolymer (UPH).
In addition to the above effects, the wettability-improving effect of the adhesive layer can be obtained by using a polyol (HA) having a relatively high molecular weight as one of raw materials of the hydroxyl-terminated Urethane Prepolymer (UPH).
The viscosity of the adhesive can be reduced and the wettability of the adhesive layer can be improved by adding a plasticizer (P) to the adhesive. In the case of using the plasticizer (P), a solution of the hydroxyl-terminated urethane prepolymer containing the plasticizer (P) may be prepared and used to produce the adhesive, or a solution of the hydroxyl-terminated urethane prepolymer containing no plasticizer (P) may be prepared and used with the plasticizer (P) to produce the adhesive. In order to easily achieve both high solid content and low viscosity of the solution of the hydroxyl-terminated urethane prepolymer, it is preferable to prepare a solution of the hydroxyl-terminated urethane prepolymer containing the plasticizer (P) and use the solution to produce an adhesive.
Further, by using the active hydrogen group-containing compound (HB) having a relatively low molecular weight as one of the raw materials of the hydroxyl-terminated Urethane Prepolymer (UPH), the effect of improving the removability of the adhesive layer can be obtained.
< polyol (HA) >
The number average molecular weight (Mn) of the polyol (HA) as the higher molecular weight component is 1000 or more, preferably 1000 to 7000, more preferably 2000 to 6000, and particularly preferably 3000 to 5000. When Mn is 1000 or more, the cohesive force of the hydroxyl-terminated Urethane Prepolymer (UPH) becomes preferable, and the initial hardening property of the adhesive and the wettability of the adhesive layer become good. When Mn is 7000 or less, the molecular weight of the hydroxyl-terminated Urethane Prepolymer (UPH) becomes preferable, and the pot life of the adhesive becomes good.
The kind of the polyol (HA) is not particularly limited, and there may be mentioned: polyester polyols, polyether polyols, polyacrylic polyols, polycaprolactone polyols, polycarbonate polyols, castor oil polyols, and the like. Among these, polyester polyols, polyether polyols, and combinations thereof are preferable. From the viewpoint of wettability of the adhesive layer, the one or more polyols (HA) more preferably include a polyether polyol having a moderate cohesive force.
As the polyester polyol, a known polyester polyol can be used, and a compound (esterified product) obtained by an esterification reaction of one or more polyol components and one or more acid components can be mentioned.
As the polyol component of the raw material, there can be mentioned: ethylene Glycol (EG), Propylene Glycol (PG), diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 2-ethyl-1, 3-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, 2-methyl-1, 8-octanediol, 1, 8-decanediol, octadecanediol, glycerol, trimethylolpropane, pentaerythritol, hexanetriol, and the like.
As the acid component of the raw material, there can be mentioned: succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1, 12-dodecanedioic acid, 1, 14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1, 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 4' -biphenyldicarboxylic acid, and acid anhydrides thereof.
As the polyether polyol, known polyether polyols can be used, and examples thereof include compounds (addition polymers) obtained by addition polymerization of one or more oxirane compounds using an active hydrogen group-containing compound having two or more active hydrogen groups in one molecule as an initiator.
Examples of the initiator include hydroxyl group-containing compounds and amines. Specifically, there may be mentioned: difunctional initiators such as Ethylene Glycol (EG), Propylene Glycol (PG), 1, 4-butanediol, neopentyl glycol, butylethylpentanediol, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine; trifunctional initiators such as glycerin, trimethylolpropane and triethanolamine; tetrafunctional initiators such as pentaerythritol, ethylenediamine, and aromatic diamines; pentafunctional initiators such as diethylenetriamine, and the like.
Examples of the oxirane compound include: alkylene Oxide (AO) such as Ethylene Oxide (EO), Propylene Oxide (PO), and Butylene Oxide (BO); tetrahydrofuran (THF), and the like.
The polyether polyol is preferably an alkylene oxide adduct of an active hydrogen group-containing compound (also referred to as "polyoxyalkylene polyol"). Among them, bifunctional polyether polyols such as polyethylene glycol (PEG), polypropylene glycol (PPG), and polytetramethylene glycol are preferable; and trifunctional polyether polyols such as alkylene oxide adducts of glycerin.
< Compound (HB) containing active Hydrogen group >
The number average molecular weight (Mn) of the active hydrogen group-containing compound (HB) as the lower molecular weight component is less than 1000, preferably 50 to 900, more preferably 50 to 300, and particularly preferably 50 to 200. As described above, since the hydroxyl-terminated Urethane Prepolymer (UPH) having a relatively low molecular weight generally tends to have poor initial curability, the initial curability can be improved by using the active hydrogen group-containing compound (HB) as a relatively low molecular weight component as one of the raw materials of the hydroxyl-terminated Urethane Prepolymer (UPH).
As the active hydrogen group, there can be mentioned: hydroxyl group, mercapto group, and amino group (in the present specification, amino group includes imino group unless otherwise specified). As the active hydrogen group-containing compound (HB), there can be mentioned: polyols having a plurality of hydroxyl groups in one molecule, polyamines having a plurality of amino groups in one molecule, aminoalcohols having an amino group and a hydroxyl group in one molecule, polythiols having a plurality of mercapto groups in one molecule, and the like. These may be used singly or in combination. The active hydrogen group-containing compound (HB) may be a non-polymer or a polymer.
Among them, polyhydric alcohols are preferable. Since polyamines and polythiols have high reactivity and a short pot life, when these are used, they are preferably used in combination with a polyol. In addition, in the case where the polyol contains a secondary hydroxyl group, the initial hardening property of the urethane adhesive is not improved, and therefore, from the viewpoint of pot life and initial hardening property, the active hydrogen group-containing compound (HB) preferably contains a primary hydroxyl group having appropriate reactivity as an active hydrogen group, and more preferably contains only a primary hydroxyl group as an active hydrogen group.
Examples of non-polymeric polyols include: ethylene Glycol (EG), Propylene Glycol (PG), diethylene glycol, triethylene glycol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 2-ethyl-1, 3-hexanediol (also referred to as "1, 3-octanediol"), 1, 8-octanediol, 1, 9-nonanediol, 2-methyl-1, 8-octanediol, 1, 8-decanediol, octadecanediol, glycerol, Trimethylolpropane (TMP), pentaerythritol, 1, 9-nonanediol, Trimethylolpropane (TMP), and the like, And hexanetriol, etc.
As the polyol which can be used as the polymer of the active hydrogen group-containing compound (HB), there can be mentioned: polyester polyols, polyether polyols, polyacrylic polyols, polycaprolactone polyols, polycarbonate polyols, castor oil polyols, and the like. Among these, polyester polyols, polyether polyols, and combinations thereof are preferable.
The polyester polyol and the polyether polyol are exemplified in the same manner as those exemplified for the polyol (HA).
As polyamines usable as the active hydrogen group-containing compound (HB), there can be mentioned: ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine, 1, 7-heptylenediamine, 1, 8-octylenediamine, 1, 9-nonylenediamine, 1, 10-decyldiamine, 1, 12-dodecyldiamine, 1, 14-tetradecylenediamine, 1, 16-hexadecyldiamine, hexamethylenediamine, trimethylhexamethylenediamine, iminobispropylamine, methyliminobispropylamine, 1, 5-diamino-2-methylpentane, isophoronediamine, 1, 3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3, 3, 5-trimethyl-cyclohexylamine, 1, 4-butylenediamine, 1, 5-tetramethylenediamine, 1, 6-dodecyldiamine, 1, 14-tetradecylenediamine, 1, 16-hexadecyldiamine, hexamethylenediamine, trimethylhexamethylenediamine, iminobispropylamine, 1, 5-trimethyl-cyclohexylamine, 3-aminopropane, 3-aminomethyl-cyclohexylamine, 2-diamine, and mixtures thereof, Aliphatic polyamines such as dimethylene diamine (MXDA), hexamethylene diamine carbamate, diethylene triamine, triethylene tetramine, tetraethyl pentamine, and pentaethylene hexamine with a norbornane skeleton; aromatic polyamines such as 3, 3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA), 4 '-diaminodiphenylmethane, 2, 4' -diaminodiphenylmethane, 3 '-diaminodiphenylmethane, 3, 4' -diaminodiphenylmethane, 2 '-diaminobiphenyl, 3' -diaminobiphenyl, 2, 4-diaminophenol, 2, 5-diaminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2, 3-tolylenediamine, 2, 4-tolylenediamine, 2, 5-tolylenediamine, 2, 6-tolylenediamine, 3, 4-tolylenediamine, and diethyltolylenediamine.
As the amino alcohol that can be used as the active hydrogen group-containing compound (HB), there can be mentioned: monoamines having a hydroxyl group such as monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tris (hydroxymethyl) aminomethane, and 2-amino-2-ethyl-1, 3-propanediol; diamines having a hydroxyl group such as N- (2-hydroxypropyl) ethanolamine, and the like.
As polythiols usable as the active hydrogen group-containing compound (HB), there can be mentioned: methanedithiol, 1, 3-butanedithiol, 1, 4-butanedithiol, 2, 3-butanedithiol, 1, 2-benzenedithiol, 1, 3-benzenedithiol, 1, 4-benzenedithiol, 1, 10-decanedithiol, 1, 2-ethanedithiol, 1, 6-hexanedithiol, 1, 9-nonanedithiol, 1, 8-octanedithiol, 1, 5-pentanedithiol, 1, 2-propanedithiol, 1, 3-propanedithiol, toluene-3, 4-dithiol, 3, 6-dichloro-1, 2-benzenedithiol, 1, 5-naphthalenedithiol, 1, 2-benzenedimethanethiol, 1, 3-benzenedimethanethiol, 1, 4-benzenedimethanethiol, 1, 3-benzenedithiol, 1, 4-benzenedimethanethiol, 1, 2-benzenedithiol, 1, 2-benzenedimethanethiol, 1, 2, 1, 2, 1, and benzene dimethanethiol, 4, 4' -thiobisbenzenethiol, 2, 5-dimercapto-1, 3, 4-thiadiazole, 1, 8-dimercapto-3, 6-dioxaoctane, 1, 5-dimercapto-3-thiapentane, 2-di-n-butylamino-4, 6-dimercapto-s-triazine, and thiol group-terminated polymers (polythioether polymers and the like).
The number of functional groups (number of hydroxyl groups) of one or more polyols (HA) is arbitrary, and a plurality of polyols (HA) having different numbers of functional groups may be used in combination as necessary. Similarly, the number of functional groups (number of active hydrogen groups) of one or more active hydrogen group-containing compounds (HB) is arbitrary, and a plurality of active hydrogen group-containing compounds (HB) having different numbers of functional groups may be used in combination as necessary.
The one or more polyols (HA) may comprise difunctional polyols and/or trifunctional or greater polyols. Likewise, the one or more active hydrogen group-containing compounds (HB) may contain a difunctional active hydrogen group-containing compound and/or a trifunctional or more active hydrogen group-containing compound. In general, the bifunctional active hydrogen group-containing compound has two-dimensional crosslinkability and can impart appropriate flexibility to the adhesive layer. The trifunctional or higher active hydrogen group-containing compound has three-dimensional crosslinkability and can impart an appropriate hardness to the adhesive layer. By selecting the number of functional groups (the number of active hydrogen groups) of each of the one or more polyols (HA) and the one or more active hydrogen group-containing compounds (HB), the properties of the urethane adhesive, such as adhesive force, cohesive force, and removability, can be adjusted. The number of functional groups of each material can be selected according to the application, etc., so that the properties such as adhesive force, cohesive force, and removability are in a preferable range.
The one or more polyols (HA) preferably include a trifunctional or higher polyol, and more preferably include a trifunctional or higher polyether polyol, from the viewpoint of facilitating both the adhesion and removability. The one or more active hydrogen group-containing compounds (HB) are preferably difunctional active hydrogen group-containing compounds in terms of ease of compatibility between reaction stability and cohesive force.
The plurality of active hydrogen group-containing compounds (HX) that are the starting materials of the hydroxyl-terminated Urethane Prepolymer (UPH) may contain one or more known active hydrogen group-containing compounds other than the polyol (HA) and the active hydrogen group-containing compound (HB).
< polyisocyanate (N) >
As the polyisocyanate (N), known polyisocyanates (N) can be used, and there can be mentioned: aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate.
Examples of the aromatic polyisocyanate include: 1, 3-phenylene diisocyanate, 4 '-diphenyl diisocyanate, 1, 4-phenylene diisocyanate, 4' -diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4 '-toluidine diisocyanate, 2, 4, 6-triisocyanate toluene, 1, 3, 5-triisocyanate benzene, dianisidine diisocyanate, 4' -diphenyl ether diisocyanate, and 4, 4 ', 4 "-triphenylmethane triisocyanate, omega' -diisocyanate-1, 3-dimethylbenzene, omega '-diisocyanate-1, 4-dimethylbenzene, omega' -diisocyanate-1, 4-diethylbenzene, 1, 4-tetramethylxylylene diisocyanate, and 1, 3-tetramethylxylylene diisocyanate.
Examples of the aliphatic polyisocyanate include: trimethylene diisocyanate, tetramethylene diisocyanate, Hexamethylene Diisocyanate (HDI), pentamethylene diisocyanate, 1, 2-propylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate, dodecamethylene diisocyanate, and 2, 4, 4-trimethylhexamethylene diisocyanate, and the like.
Examples of the alicyclic polyisocyanate include: isophorone diisocyanate (IPDI), 1, 3-cyclopentane diisocyanate, 1, 3-cyclohexane diisocyanate, 1, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), and 1, 4-bis (isocyanotomethyl) cyclohexane, and the like.
Further, as the polyisocyanate, there can be mentioned: trimethylolpropane adduct, biuret (biuret) form, allophanate (allophanate) form, trimer (the trimer including an isocyanurate ring) form, and the like.
The polyisocyanate (N) is preferably 4, 4' -diphenylmethane diisocyanate, Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), or the like. As will be described in detail later, the one or more polyisocyanates (N) preferably comprise isophorone diisocyanate (IPDI).
Preferred raw material formulations of the hydroxyl-terminated Urethane Prepolymer (UPH) are as follows.
The raw material compounding ratio is preferably determined so that the ratio (NCO/H) of the number of moles of isocyanate groups (NCO) in the polyisocyanate (N) to the total number of moles of active hydrogen groups (H) in the plurality of active hydrogen group-containing compounds (HX) is 0.20 to 0.84, more preferably 0.40 to 0.80. The following tendency is exhibited: the closer the NCO/H is to 1, the more likely it is to gel during synthesis of a hydroxyl-terminated Urethane Prepolymer (UPH). When the NCO/H ratio is 0.84 or less, gelation at the time of synthesizing a hydroxyl-terminated Urethane Prepolymer (UPH) can be effectively suppressed.
The amount of the one or more active hydrogen group-containing compounds (HB) is preferably 0.5 to 40 parts by mass, more preferably 2 to 40 parts by mass, and particularly preferably 1 to 25 parts by mass, relative to 100 parts by mass of the one or more polyols (HA), from the viewpoint of achieving a high solid content concentration and low viscosity of the adhesive and also improving the initial hardenability of the adhesive.
The amount of the one or more polyisocyanates (N) is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, per 100 parts by mass of the one or more polyols (HA), from the viewpoint of achieving a high solid content concentration and a low viscosity of the adhesive and also improving the initial hardening properties of the adhesive.
< catalyst >
If desired, more than one catalyst may be used in the polymerization of the hydroxyl-terminated Urethane Prepolymer (UPH). As the catalyst, a known catalyst can be used, and examples thereof include tertiary amine compounds, organometallic compounds, and the like.
Examples of the tertiary amine compound include: triethylamine, triethylenediamine, and 1, 8-diazabicyclo (5, 4, 0) -undecene-7 (1, 8-diazabicyclo (5, 4, 0) -undecene-7, DBU), and the like.
Examples of the organometallic compound include tin compounds and non-tin compounds.
Examples of the tin-based compound include: dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate (dibutyl tin dimaleate), dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin acetate (triethyl acetate), tributyltin acetate (tributyl acetate), dioctyltin dilaurate, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate, and the like.
Examples of the non-tin compound include: titanium systems such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride; lead-based materials such as lead oleate, lead 2-ethylhexoate, lead benzoate, and lead naphthenate; iron series such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt systems such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc systems such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium-based compounds such as zirconium naphthenate.
The kind and amount of the catalyst to be added can be suitably designed within a range in which the reaction proceeds well.
When a plurality of active hydrogen group-containing compounds (HX) are used together, gelation or clouding of the reaction solution may easily occur in a single catalyst system due to the difference in reactivity between the active hydrogen group-containing compounds (HX). In such a case, by using two catalysts, it is easy to control the reaction (e.g., reaction rate, etc.), so that the problem can be solved. The combination of the two catalysts is not particularly limited, and there may be exemplified: tertiary amine/organic metal system, tin system/non-tin system, and tin system/tin system, etc. Tin-based/tin-based is preferred, and dibutyltin dilaurate and tin 2-ethylhexanoate are more preferred.
The mass ratio of tin 2-ethylhexanoate to dibutyltin dilaurate (tin 2-ethylhexanoate/dibutyltin dilaurate) is not particularly limited, but is preferably more than 0 and less than 1, and more preferably 0.2 to 0.6. If the mass ratio is less than 1, the balance of the catalyst activity is good, gelation and clouding of the reaction solution are effectively suppressed, and the polymerization stability is further improved.
< solvent >
If necessary, one or more solvents may be used for the polymerization of the hydroxyl-terminated Urethane Prepolymer (UPH). As the solvent, a known solvent can be used, and generally, an organic solvent such as methyl ethyl ketone, ethyl acetate, toluene, xylene, or acetone can be used.
The solution of the hydroxyl group-containing terminal urethane prepolymer of the present invention can have a low viscosity even at a high solid content concentration, and therefore the amount of the organic solvent to be used can be reduced. The content of the organic solvent in the solution of the hydroxyl group-containing terminal urethane prepolymer of the present invention is preferably 20% by mass or less, more preferably 10% by mass or less, and may be 0% by mass. The amount of Volatile Organic Compound (VOC) used in the solution of the hydroxyl group-containing terminal urethane prepolymer of the present invention is small, and is preferable from the viewpoint of environmental aspects and the like.
< method for producing solution of hydroxyl group-containing terminal urethane prepolymer >
The solution of the hydroxyl group-containing terminal urethane prepolymer can be produced by copolymerizing one or more active hydrogen group-containing compounds (HX) with one or more polyisocyanates (N) in the presence of one or more solvents and optionally one or more catalysts. The polymerization method is not particularly limited, and known polymerization methods such as bulk polymerization and solution polymerization can be used. The polymerization reaction may be carried out in one stage or in multiple stages.
The reaction temperature when the catalyst is used is preferably less than 100 ℃, more preferably 50 to 95 ℃, and particularly preferably 60 to 85 ℃. If the reaction temperature is 100 ℃ or higher, the following concerns may arise: it is difficult to control the reaction rate, polymerization stability, etc., and it is difficult to produce a hydroxyl-terminated Urethane Prepolymer (UPH) having a desired molecular weight. The reaction temperature when no catalyst is used is preferably 100 ℃ or higher, more preferably 110 ℃ or higher.
Hereinafter, a preferred production method of a hydroxyl-terminated urethane prepolymer (UPH-S) which is a reaction product of a plurality of kinds of active hydrogen group-containing compounds (HX) containing at least one kind of polyol (HA) having Mn of 1000 or more, preferably 1000 to 7000, and at least one kind of active hydrogen group-containing compound (HB) having Mn of less than 1000, preferably 50 to 900, and one or more kinds of polyisocyanate (N) will be described.
As the polymerization order of the hydroxyl-terminated urethane prepolymer (UPH-S), there may be mentioned:
sequence 1) a sequence in which one or more polyols (HA), one or more active hydrogen group-containing compounds (HB), one or more polyisocyanates (N), optionally one or more catalysts, and optionally one or more solvents are charged into a flask together;
sequence 2) a sequence in which one or more polyols (HA), one or more active hydrogen group-containing compounds (HB), optionally one or more catalysts, and optionally one or more solvents are charged into a flask, and one or more polyisocyanates (N) are added dropwise thereto;
sequence 3) A procedure in which one or more polyols (HA), one or more polyisocyanates (N), optionally one or more catalysts, and optionally one or more solvents are charged into a flask together, one or more polyisocyanates (N) and one or more polyols (HA) are reacted at an excess isocyanate group ratio to form an isocyanate group-terminated urethane prepolymer (UPN-S), and then one or more active hydrogen group-containing compounds (HB) are added.
In the sequences 1) and 2), the polyol (HA) having a higher molecular weight and the active hydrogen group-containing compound (HB) having a lower molecular weight are simultaneously mixed with the polyisocyanate (N). In the method, the following steps are performed: the active hydrogen group-containing compound (HB) having a lower molecular weight and a higher reactivity reacts preferentially with the polyisocyanate (N) than the polyol (HA) having a higher molecular weight and a lower reactivity. In such a case, there is a fear that: the relatively high molecular weight polyol (HA) having low reactivity remains in an unreacted state, and the reaction liquid becomes cloudy. When the condition that the number of moles of isocyanate groups is excessive relative to the total number of moles of active hydrogen groups is set to eliminate the relatively high molecular weight polyol (HA) remaining in an unreacted state, there is a concern that: causing an undesirable reaction of the isocyanate group-terminated urethane prepolymer formed by the initial reaction of the lower molecular weight active hydrogen group-containing compound (HB) with the polyisocyanate (N) with the highly reactive lower molecular weight active hydrogen group-containing compound (HB), thereby causing gelation of the reaction liquid.
The sequence 3) is preferable from the viewpoint of easy control of the reaction. The aggregation using the order includes: a step of reacting one or more polyols (HA) with one or more polyisocyanates (N) at a ratio of excess isocyanate groups to produce isocyanate group-terminated Urethane Prepolymers (UPN); and a step of reacting the obtained isocyanate group-terminated Urethane Prepolymer (UPN) with one or more active hydrogen group-containing compounds (HB).
In the order 3), in a state where the active hydrogen group-containing compound (HB) of lower molecular weight does not coexist, only the polyol (HA) of higher molecular weight having low reactivity is reacted with the polyisocyanate (N), and then the obtained isocyanate group-terminated Urethane Prepolymer (UPN) is reacted with the active hydrogen group-containing compound (HB). In the above method, the desired hydroxyl-terminated urethane prepolymer (UPH-S) can be stably synthesized while suppressing gelation and clouding of the reaction solution.
Therefore, the hydroxyl-terminated urethane prepolymer (UPH-S) is preferably a reaction product of an isocyanate-terminated Urethane Prepolymer (UPN), which is a reaction product of a polyol (HA) and a polyisocyanate (N), and an active hydrogen group-containing compound (HB).
In sequence 3), the one or more polyisocyanates (N) preferably comprise isophorone diisocyanate (IPDI). In this case, the reaction can be easily controlled and a desired hydroxyl-terminated urethane prepolymer (UPH-S) can be stably synthesized.
(polyfunctional isocyanate Compound (I))
As the polyfunctional isocyanate compound (I), a known polyfunctional isocyanate compound (I) can be used, and compounds exemplified as the polyisocyanate (N) which is a raw material of the hydroxyl-terminated Urethane Prepolymer (UPH) (specifically, aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate, and trimethylolpropane adduct/biuret/urea/trimer thereof) can be used.
(plasticizer (P))
The adhesives of the invention may optionally contain more than one plasticizer (P). The plasticizer (P) may function as a diluent together with the solvent. The addition of the plasticizer (P) to the adhesive of the present invention is preferable because low viscosity can be achieved even at a high solid content concentration. When the adhesive of the present invention contains the plasticizer (P), the adhesive layer has good wettability with respect to an adherend such as glass, and an effect of suppressing air bubbles from being drawn into the adhesion interface when the adhesive sheet is adhered to the adherend can be obtained.
The amount of the plasticizer (P) is preferably 0 to 200 parts by mass, more preferably 20 to 200 parts by mass, with respect to 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH). The amount of the plasticizer (P) is particularly preferably 50 to 200 parts by mass or 20 to 150 parts by mass, and most preferably 50 to 150 parts by mass, relative to 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH).
The plasticizer (P) is not particularly limited, and is preferably an organic acid ester having a molecular weight of 250 to 1,000 from the viewpoint of compatibility with other components.
Examples of esters of mono-or polybasic acids with alcohols include: isostearyl laurate, isopropyl myristate, isocetyl myristate, octyldodecyl myristate, isostearyl palmitate, isocetyl stearate, octyldodecyl oleate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, diisodecyl adipate, diisostearyl adipate, dibutyl sebacate, diisocetyl sebacate, tributyl acetylcitrate, tributyl trimellitate, trioctyl trimellitate, trihexyl trimellitate, triolenyl trimellitate, and triisocetyl trimellitate.
Examples of esters of other acids with alcohols include: esters of unsaturated fatty acids or branched acids such as myristoleic acid, oleic acid, linoleic acid, linolenic acid, isopalmitic acid, and isostearic acid with alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, and sorbitan.
Examples of esters of mono-or polybasic acids with polyalkylene glycols include: polyethylene glycol dihexanoate, polyethylene glycol di-2-ethylhexanoate, polyethylene glycol dilaurate, polyethylene glycol dioleate, and diethylene glycol monomethyl adipate.
The molecular weight (formula weight or Mn) of the organic acid ester is preferably 250 to 1,000, more preferably 400 to 900, and particularly preferably 500 to 850, from the viewpoint of improving wettability. When the molecular weight is 250 or more, the heat resistance of the adhesive layer becomes good. When the molecular weight is 1,000 or less, the wettability of the adhesive becomes good, and the adhesive can be effectively made to have a low viscosity.
(beta-diketone compound (X))
The adhesive of the present invention may optionally contain one or more than one beta-diketone compound (X). The β -diketone compound (X) is not particularly limited, and includes: acetylacetone, 2, 4-pentanedione, 3-methyl-2, 4-pentanedione, 2, 4-hexanedione, 1, 3-cyclohexanedione, 2-dimethyl-3, 5-hexanedione, 2, 4-heptanedione, 3, 5-heptanedione, 2, 6, 6-tetramethyl-3, 5-heptanedione, 1, 3-cycloheptanedione, 2, 4-octanedione, 2, 7-trimethyl-3, 5-octanedione, 2, 4-nonanedione, 3-methyl-2, 4-nonanedione, 2-methyl-4, 6-nonanedione, 1-phenyl-1, 3-butanedione, and spirodecanedione, and the like. Among them, acetylacetone and the like are preferable. The β -diketone compound (X) such as acetylacetone functions as a hardening retarder, and the pot life can be favorably adjusted by adding it to the adhesive.
(solvent)
The adhesives of the invention may optionally contain more than one solvent. As the solvent, known solvents can be used, and examples thereof include: organic solvents such as methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone.
The adhesive of the present invention has a relatively high solid content concentration and has good coating suitability because of having a relatively low viscosity at the coating time, and therefore the amount of the organic solvent to be used can be reduced.
The content of the organic solvent in the adhesive of the present invention is preferably 20% by mass or less, more preferably 10% by mass or less, and may be 0% by mass. The adhesive of the present invention is preferably used in a small amount of Volatile Organic Compounds (VOC) from the viewpoint of environmental aspects.
(anti-deterioration agent)
The adhesive of the present invention may optionally contain more than one anti-deterioration agent. This can suppress deterioration of various properties due to long-term use of the adhesive layer. As the deterioration preventing agent, there can be mentioned: hydrolysis resistance agents, antioxidants, ultraviolet absorbers, light stabilizers, and the like.
< hydrolysis resistance agent >
In the case where a carboxyl group is generated by hydrolysis of the adhesive layer under a high-temperature and high-humidity environment, a hydrolysis resistant agent may be used to block the carboxyl group. As hydrolysis resistance agents, there can be mentioned: carbodiimide, isocyanate, oxazoline, and epoxy. Among them, a carbodiimide type is preferable from the viewpoint of the hydrolysis suppressing effect.
The carbodiimide-based hydrolysis inhibitor is a compound having one or more carbodiimide groups in one molecule.
Examples of the monocarbodiimide compound include: dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, diphenylcarbodiimide, and naphthylcarbodiimide, etc.
The polycarbodiimide compound may be produced by subjecting a diisocyanate to a decarbonylation condensation reaction in the presence of a carbodiimidization catalyst. Examples of the diisocyanate include: 4, 4 ' -diphenylmethane diisocyanate, 3 ' -dimethoxy-4, 4 ' -diphenylmethane diisocyanate, 3 ' -dimethyl-4, 4 ' -diphenylmethane diisocyanate, 4 ' -diphenylether diisocyanate, 3 ' -dimethyl-4, 4 ' -diphenylether diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 1-methoxyphenyl-2, 4-diisocyanate, isophorone diisocyanate, 4 ' -dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, and the like. Examples of the carbodiimidization catalyst include: and phospholene oxides such as 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, and 3-phospholene isomers thereof.
Examples of the isocyanate hydrolysis inhibitor include: 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4 '-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 3 '-dimethyl-4, 4' -biphenyl diisocyanate, 3 '-dimethoxy-4, 4' -biphenyl diisocyanate, 3 '-dichloro-4, 4' -biphenyl diisocyanate, 1, 5-naphthalene diisocyanate, 1, 5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1, 6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimethylhexamethylene diisocyanate, dimethylnaphthalene diisocyanate, and mixtures thereof, 1, 3-cyclohexylene diisocyanate, 1, 4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4 ' -dicyclohexylmethane diisocyanate, 3 ' -dimethyl-4, 4 ' -dicyclohexylmethane diisocyanate, and the like.
Examples of the oxazoline hydrolysis inhibitor include: 2, 2 '-o-phenylbis (2-oxazoline), 2' -m-phenylbis (2-oxazoline), 2 '-p-phenylbis (4-methyl-2-oxazoline), 2' -m-phenylbis (4-methyl-2-oxazoline), 2 '-p-phenylbis (4, 4' -dimethyl-2-oxazoline), 2 '-m-phenylbis (4, 4' -dimethyl-2-oxazoline), 2 '-ethylidenebis (2-oxazoline), 2' -tetramethylenebis (2-oxazoline), 2 '-hexamethylenebis (2-oxazoline), 2' -octamethylenebis (2-oxazoline), 2, 2 '-ethylenebis (4-methyl-2-oxazoline), and 2, 2' -diphenylenebis (2-oxazoline).
Examples of the epoxy hydrolysis inhibitor include: diglycidyl ethers of aliphatic diols such as 1, 6-hexanediol, neopentyl glycol, and polyalkylene glycol; polyglycidyl ethers of aliphatic polyhydric alcohols such as sorbitol, sorbitan, polyglycerol, pentaerythritol, diglycerol, glycerol, and trimethylolpropane; polyglycidyl ethers of alicyclic polyols such as cyclohexanedimethanol; diglycidyl esters or polyglycidyl esters of aliphatic or aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, adipic acid, and sebacic acid; diglycidyl ethers or polyglycidyl ethers of polyhydric phenols such as resorcinol, bis- (p-hydroxyphenyl) methane, 2, 2-bis- (p-hydroxyphenyl) propane, tris- (p-hydroxyphenyl) methane, and 1, 1, 2, 2-tetrakis (p-hydroxyphenyl) ethane; n-glycidyl derivatives of amines such as N, N-diglycidylaniline, N-diglycidyltoluidine, and N, N' -tetraglycidyl-bis- (p-aminophenyl) methane; triglycidyl derivatives of aminophenols; triglycidyl tris (2-hydroxyethyl) isocyanurate, and triglycidyl isocyanurate; epoxy resins such as o-cresol type epoxy resins and phenol novolac type epoxy resins.
The amount of the hydrolysis resistant agent to be added is not particularly limited, and is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4.5 parts by mass, and particularly preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH).
< antioxidant >
Examples of the antioxidant include a radical scavenger and a peroxide decomposer. Examples of the radical scavenger include phenol compounds and amine compounds. Examples of the peroxide decomposer include sulfur compounds and phosphorus compounds.
Examples of the phenolic compound include: 2, 6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2, 6-di-tert-butyl-4-ethylphenol, stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2 '-methylenebis (4-methyl-6-tert-butylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), 4 '-thiobis (3-methyl-6-tert-butylphenol), 4' -butylidenebis (3-methyl-6-tert-butylphenol), 3, 9-bis [1, 1-dimethyl-2- [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ]2, 4, 8, 10-tetraoxaspiro [5, 5] undecane, phenylpropionic acid, 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy-, C7-C9 side chain alkyl ester, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [ methylene-3- (3 ', 5' -di-t-butyl-4 '-hydroxyphenyl) propionate ] methane, ethylene glycol bis [3, 3' -bis- (4 '-hydroxy-3' -t-butylphenyl) butyrate ], 1, 3, 5-tris (3 ', 5 ' -di-tert-butyl-4 ' -hydroxybenzyl) -S-triazine-2, 4, 6- (1H, 3H, 5H) trione, tocopherol, and the like.
Examples of the sulfur-based antioxidant include: dilauryl 3, 3 ' -thiodipropionate, dimyristyl 3, 3 ' -thiodipropionate, distearyl 3, 3 ' -thiodipropionate, and the like.
Examples of the phosphorus-based compound include: triphenyl phosphite, diphenylisodecyl phosphite, 4' -butylidene-bis (3-methyl-6-tert-butylphenyl ditridecyl) phosphite, cycloneopentanetetraylbis (octadecyl phosphite), tris (nonylphenyl) phosphite, tris (monononylphenyl) phosphite, tris (dinonylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3, 5-di-tert-butyl-4-hydroxybenzyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9, 10-dihydro-9-oxa-10-phosphaphenanthrene, phosphorus, Tris (2, 4-di-tert-butylphenyl) phosphite, cycloneopentanetetraylbis (2, 6-di-tert-butyl-4-methylphenyl) phosphite, and octyl 2, 2-methylenebis (4, 6-di-tert-butylphenyl) phosphite.
Thermal degradation of the hydroxyl-terminated Urethane Prepolymer (UPH) is prevented by the use of an antioxidant. In addition, the bleed-out of the plasticizer (P) from the adhesive layer when the plasticizer (P) is used can be effectively suppressed.
The amount of the antioxidant to be added is not particularly limited, but is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and particularly preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH).
As the antioxidant, from the viewpoint of stability and antioxidant effect, it is preferable to use one or more phenol compounds as the radical scavenger, and more preferably to use one or more phenol compounds as the radical scavenger in combination with one or more phosphorus compounds as the peroxide decomposer. In addition, it is particularly preferable to use a phenol compound as a radical scavenger and a phosphorus compound as a peroxide decomposer in combination as the antioxidant, and to use these antioxidants and the hydrolysis resistance agent in combination.
< ultraviolet absorber >
Examples of the ultraviolet absorber include: benzophenone-based compounds, benzotriazole-based compounds, salicylic acid-based compounds, oxalanilide-based compounds, cyanoacrylate-based compounds, triazine-based compounds, and the like.
The amount of the ultraviolet absorber added is not particularly limited, but is preferably 0.01 to 3 parts by mass, more preferably 0.1 to 2.5 parts by mass, and particularly preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH).
< light stabilizer >
Examples of the light stabilizer include hindered amine compounds and hindered piperidine compounds. The amount of the light stabilizer to be added is not particularly limited, but is preferably 0.01 to 2 parts by mass, more preferably 0.1 to 1.5 parts by mass, and particularly preferably 0.2 to 1 part by mass, based on 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH).
(antistatic agent (AS agent))
The adhesive of the present invention may optionally contain more than one antistatic agent (AS agent). As the antistatic agent, there may be mentioned: inorganic salts, polyol compounds, ionic liquids, ionic solids, surfactants, and the like, and among them, ionic liquids and/or ionic solids are preferable. The "ionic liquid" is also referred to as an ambient temperature molten salt, and is a salt having fluidity at 25 ℃.
Examples of the inorganic salt include: sodium chloride, potassium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, ammonium sulfate, potassium nitrate, sodium carbonate, sodium thiocyanate and the like.
Examples of the polyol compound include: propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, trimethylolpropane, pentaerythritol, and the like.
Examples of the ionic liquid containing an imidazolium ion include: 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, 1, 3-dimethylimidazolium bis (trifluoromethylsulfonyl) imide, and 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide.
Examples of the ionic liquid containing a pyridinium ion include: 1-methylpyridinium bis (trifluoromethylsulfonyl) imide, 1-butylpyridinium bis (trifluoromethylsulfonyl) imide, 1-hexylpyridinium bis (trifluoromethylsulfonyl) imide, 1-octylpyridinium bis (trifluoromethylsulfonyl) imide, 1-hexyl-4-methylpyridinium bis (trifluoromethylsulfonyl) imide, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis (trifluoromethylsulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methylpyridinium bis (perfluoroethylsulfonyl) imide, and 1-methylpyridinium bis (perfluorobutylsulfonyl) imide, and the like.
Examples of the ionic liquid containing an ammonium ion include: trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, tri-N-butylmethylammonium bis (trifluoromethanesulfonyl) imide, and the like.
Further, commercially available ionic liquids such as pyrrolidinium salts, phosphonium salts, and sulfonium salts can be suitably used.
The ionic solid is a salt of a cation and an anion, as in the case of the ionic liquid, but shows a solid state at 25 ℃ under normal pressure. The cation is preferably an alkali metal ion, a phosphonium ion, a pyridinium ion, an ammonium ion, or the like.
Examples of the ionic solid containing an alkali metal ion include: lithium bis-fluorosulfonyl imide, lithium bis-trifluoromethylsulfonyl imide, lithium bis-pentafluoroethylsulfonyl imide, lithium bis-heptafluoropropylsulfonyl imide, lithium bis-nonane fluorobutylsulfonyl imide, sodium bis-fluorosulfonyl imide, sodium bis-trifluoromethylsulfonyl imide, sodium bis-pentafluoroethylsulfonyl imide, sodium bis-heptafluoropropylsulfonyl imide, sodium bis-nonane fluorobutylsulfonyl imide, potassium bis-fluorosulfonyl imide, potassium bis-trifluoromethylsulfonyl imide, potassium bis-pentafluoroethylsulfonyl imide, potassium bis-heptafluoropropylsulfonyl imide, and potassium bis-nonane fluorobutylsulfonyl imide, and the like.
Examples of the ionic solid containing a phosphonium ion include: tetrabutylphosphonium difluoride sulfonyl imide, tetrabutylphosphonium bistrifluoromethylsulfonyl imide, tetrabutylphosphonium bistrifluoroethylsulfonyl imide, tetrabutylphosphonium bistheptafluoropropylsulfonyl imide, tetrabutylphosphonium bistonofluoroalkylfluorobutylsulfonyl imide, tributylhexadecylphosphonium bistrifluorosulfonyl imide, tributylhexadecylphosphonium bistrifluoromethylsulfonyl imide, tributylhexadecylphosphonium bistrifluoroethylsulfonyl imide, tributylhexadecyl phosphonium bis-heptafluoropropylsulfonyl imide, tributylhexadecyl phosphonium bis-nonane fluorobutylsulfonyl imide, tetraoctyl phosphonium bis-fluorosulfonyl imide, tetraoctyl phosphonium bis-trifluoromethyl sulfonyl imide, tetraoctyl phosphonium bis-pentafluoroethylsulfonyl imide, tetraoctyl phosphonium bis-heptafluoropropylsulfonyl imide, and tetraoctyl phosphonium bis-nonane fluorobutylsulfonyl imide, and the like.
Examples of the ionic solid containing a pyridinium ion include: 1-hexadecyl-4-methylpyridinium difluorosulfonyl imide, 1-hexadecyl-4-methylpyridinium bistrifluoromethylsulfonyl imide, 1-hexadecyl-4-methylpyridinium dipentafluoroethylsulfonyl imide, 1-hexadecyl-4-methylpyridinium bispentafluoropropylsulfonyl imide, and 1-hexadecyl-4-methylpyridinium dinonylfluorobutylsulfonyl imide, and the like.
Examples of the ionic solid containing an ammonium ion include: lauryl trimethyl ammonium chloride, tributylmethyl bis (trifluoromethylsulfonyl) imide, tributylmethyl bis (pentafluoroethylsulfonyl) imide, tributylmethyl bis (heptafluoropropylsulfonyl) imide, tributylmethyl bis (nonane fluorobutylsulfonyl) imide, octyl tributylbis (trifluoromethylsulfonyl) imide, octyl tributyl bis (pentafluoroethylsulfonyl) imide, octyl tributyl bis (heptafluoropropylsulfonyl) imide, octyl tributyl bis (nonane fluorobutylsulfonyl) imide, tetrabutyl bis (fluorosulfonyl) imide, tetrabutyl bis (trifluoromethyl sulfonyl) imide, tetrabutyl bis (pentafluoroethylsulfonyl) imide, tetrabutyl bis (heptafluoropropylsulfonyl) imide, tetrabutyl bis (nonane fluorobutylsulfonyl) imide, and the like.
In addition, known ionic solids having cations such as pyrrolidinium ion, imidazolium ion, and sulfonium ion can be suitably used.
Surfactants are classified into low-molecular surfactants and high-molecular surfactants. Either type is nonionic, anionic, cationic, and amphoteric.
Examples of the nonionic low-molecular-weight surfactant include: glycerin fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, and fatty acid diethanolamides.
Examples of the anionic low-molecular-weight surfactant include: alkyl sulfonates, alkylbenzene sulfonates, and alkyl phosphates, and the like.
Examples of the cationic low-molecular-weight surfactant include tetraalkylammonium salts and trialkylbenzylammonium salts.
Examples of the amphoteric low-molecular-weight surfactant include alkyl betaines and alkyl imidazolium betaines.
Examples of the nonionic polymer surfactant include: polyether ester amide type, ethylene oxide-epichlorohydrin type, polyether ester type, and the like.
Examples of the anionic polymeric surfactant include polystyrene sulfonic acid type surfactants.
Examples of the cationic polymer surfactant include acrylate polymer type surfactants containing quaternary ammonium salt groups.
Examples of the amphoteric polymer surfactant include: and amino acid type amphoteric surfactants such as higher alkyl aminopropionates, and betaine type amphoteric surfactants such as higher alkyl dimethyl betaines and higher alkyl dihydroxyethyl betaines.
The amount of the antistatic agent added is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, per 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH).
(leveling agent)
The adhesive of the present invention may optionally contain a leveling agent. By adding the leveling agent, the leveling property of the adhesive layer can be improved. As the leveling agent, there can be mentioned: acrylic leveling agents, fluorine leveling agents, silicone leveling agents, and the like are preferred from the viewpoint of suppressing contamination of the adherend after re-peeling of the adhesive sheet.
The weight average molecular weight (Mw) of the leveling agent is not particularly limited, but is preferably 500 to 20,000, more preferably 1,000 to 15,000, and particularly preferably 2,000 to 10,000. When Mw is 500 or more, the amount of vaporization from the coating layer during heating and drying of the coating layer can sufficiently suppress contamination of the surroundings. When Mw is 20,000 or less, the leveling property of the adhesive layer is effectively improved.
The amount of the leveling agent is not particularly limited, and is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 1.5 parts by mass, and particularly preferably 0.1 to 1 part by mass, based on 100 parts by mass of the hydroxyl-terminated Urethane Prepolymer (UPH), from the viewpoints of suppressing contamination of an adherend after re-peeling of the adhesive sheet and improving the leveling property of the adhesive layer.
(other optional ingredients)
The adhesive of the present invention may optionally contain other optional components within a range not impairing the effects of the present invention. As other optional components, there may be mentioned: a catalyst, a resin other than the urethane resin, a filler (talc, calcium carbonate, titanium oxide, or the like), a metal powder, a colorant (pigment, or the like), a foil, a softening agent, a conductive agent, a silane coupling agent, a lubricant, an anticorrosive agent, a heat-resistant stabilizer, a weather-resistant stabilizer, a polymerization inhibitor, an antifoaming agent, or the like.
(mixing ratio)
The adhesive of the present invention contains one or more hydroxyl-terminated Urethane Prepolymers (UPH) and one or more polyfunctional isocyanate compounds (I) as essential components, and further contains one or more optional components as required. The blending ratio of these is not particularly limited, and preferable blending ratios are as follows.
The amount of the one or more polyfunctional isocyanate compounds (I) is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, per 100 parts by mass of the one or more hydroxyl-terminated Urethane Prepolymers (UPH). When the amount of the one or more polyfunctional isocyanate compounds (I) is 3 parts by mass or more, the cohesive force of the adhesive layer becomes good, and when it is 20 parts by mass or less, the pot life becomes good.
(method for producing adhesive)
The method for producing the adhesive of the present invention is not particularly limited.
The pressure-sensitive adhesive of the present invention can be produced by adding and mixing one or more kinds of the polyfunctional isocyanate compound (I) and optionally one or more kinds of optional components to a solution of the hydroxyl group-containing terminal urethane prepolymer synthesized by a one-stage or multi-stage copolymerization reaction.
[ adhesive sheet ]
The adhesive sheet of the present invention includes a substrate sheet and an adhesive layer containing a cured product of the adhesive of the present invention. The adhesive layer may be formed on one or both sides of the substrate sheet. The exposed surface of the adhesive layer may be covered with a release sheet as necessary. Further, the release sheet may be peeled off when the adhesive sheet is attached to the adherend.
Fig. 1 is a schematic cross-sectional view of an adhesive sheet according to a first embodiment of the present invention. In fig. 1, reference numeral 10 denotes an adhesive sheet, reference numeral 11 denotes a base sheet, reference numeral 12 denotes an adhesive layer, and reference numeral 13 denotes a release sheet. The adhesive sheet 10 is a single-sided adhesive sheet having an adhesive layer formed on one side of a base sheet.
Fig. 2 is a schematic cross-sectional view of an adhesive sheet according to a second embodiment of the present invention. In fig. 2, reference numeral 20 denotes an adhesive sheet, reference numeral 21 denotes a base sheet, reference numerals 22A and 22B denote adhesive layers, and reference numerals 23A and 23B denote release sheets.
The substrate sheet is not particularly limited, and includes: resin sheet, paper, metal foil, and the like. The substrate sheet may be a laminated sheet in which any one or more layers are laminated on at least one surface of these substrate sheets. The surface of the substrate sheet on the side on which the adhesive layer is formed may be subjected to an easy adhesion treatment such as corona discharge treatment and anchor coating agent (anchor coating agent) coating, if necessary.
The resin constituting the resin sheet is not particularly limited, and includes: ester resins such as polyethylene terephthalate (PET); olefin resins such as Polyethylene (PE) and polypropylene (PP); vinyl resins such as polyvinyl chloride; amide resins such as nylon 66; urethane resin (including foam); combinations of these, and the like.
The thickness of the resin sheet other than the polyurethane sheet is not particularly limited, but is preferably 15 to 300 μm. The thickness of the polyurethane sheet (including the foam) is not particularly limited, and is preferably 20 μm to 50,000 μm.
The paper is not particularly limited, and includes: plain paper, coated paper, and the like.
The constituent metal of the metal foil is not particularly limited, and examples thereof include: aluminum, copper, combinations of these, and the like.
The release sheet is not particularly limited, and a known release sheet obtained by applying a known release treatment such as coating of a release agent to the surface of a substrate sheet such as a resin sheet or paper can be used.
The adhesive sheet can be produced by a known method.
First, the adhesive of the present invention is applied to the surface of a substrate sheet to form a coating layer containing the adhesive of the present invention. The coating method may be any known method, and examples thereof include: a roll coater method, a comma coater method, a die coater method, a reverse coater method, a screen printing method, a gravure coater method, and the like.
Next, the coating layer is dried and cured to form an adhesive layer containing a cured product of the adhesive of the present invention. The heating and drying temperature is not particularly limited, but is preferably about 60 ℃ to 150 ℃. The thickness of the adhesive layer (thickness after drying) varies depending on the application, but is preferably 0.1 to 200 μm.
Next, if necessary, a release sheet is attached to the exposed surface of the adhesive layer by a known method.
In this manner, a single-sided adhesive sheet can be produced.
By performing the above operation on both sides, a double-sided adhesive sheet can be manufactured.
In contrast to the above method, the adhesive of the present invention may be applied to the surface of a release sheet to form a coating layer containing the adhesive of the present invention, the coating layer may be dried and cured to form an adhesive layer containing a cured product of the adhesive of the present invention, and a substrate sheet may be laminated on the exposed surface of the adhesive layer.
The method for producing an adhesive sheet preferably includes: a coating step of coating an adhesive on a base sheet; a heating step of forming an adhesive layer containing a cured product of an adhesive by heating and drying the formed coating layer; a winding step of winding the obtained adhesive sheet around a core to form an adhesive sheet roll; and a curing step of curing the adhesive sheet roller.
As described above, according to the present invention, it is possible to provide a solution of a hydroxyl group-containing terminal urethane prepolymer for an adhesive, which has a relatively low viscosity and a relatively high solid content concentration, while reducing the amount of an organic solvent used. According to the present invention, there is provided a solution of a hydroxyl group-containing terminal urethane prepolymer for an adhesive, which has a solid content concentration of 80 mass% or more, preferably 85 mass% or more, particularly preferably 90 mass% or more, and most preferably 95 mass% or more, and which has a viscosity at 25 ℃ of 8000 mPas or less, preferably 7000 mPas or less, more preferably 6000 mPas or less, and particularly preferably 5000 mPas or less after standing at 25 ℃ for 1 hour immediately after production.
Further, according to the present invention, an adhesive which is reduced in the amount of the organic solvent used, has a relatively high solid content concentration, and has a relatively low viscosity at the time of application to have good applicability to application can be provided. According to the present invention, there can be provided an adhesive having a solid content concentration of preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more, and having a viscosity at 25 ℃ after leaving at 25 ℃ for 3 hours immediately after production of preferably 8000 mPas or less, more preferably 7000 mPas or less, and particularly preferably 5000 mPas or less. By setting the viscosity at 25 ℃ after standing at 25 ℃ for 3 hours immediately after the preparation to the range, good coating suitability can be obtained.
In order to achieve a high solid content concentration and a low viscosity of the adhesive, the hydroxyl-terminated Urethane Prepolymer (UPH) used in the present invention is preferably a low molecular weight as compared with a conventional general hydroxyl-terminated urethane prepolymer.
In order to achieve a high solid content and a low viscosity of the adhesive and to improve the initial hardening properties of the adhesive, the hydroxyl-terminated Urethane Prepolymer (UPH) is preferably a hydroxyl-terminated urethane prepolymer (UPH-S) which is a reaction product of one or more polyisocyanates (N) and a plurality of active hydrogen group-containing compounds (HX) containing one or more polyols (HA) having Mn of 1000 or more, preferably 1000 to 7000, and one or more active hydrogen group-containing compounds (HB) having Mn of less than 1000, preferably 50 to 900.
By adjusting the mass ratio of one or more polyols (HA) and one or more polyisocyanates (N) as higher molecular weight components, the number average molecular weight (Mn) of the hydroxyl-terminated Urethane Prepolymer (UPH) can be made smaller, and a high solid content concentration and a low viscosity of the adhesive can be achieved. In general, since a lower molecular weight hydroxyl-terminated Urethane Prepolymer (UPH) tends to have poor initial curability, the initial curability can be improved by using a lower molecular weight active hydrogen group-containing compound (HB) as one of the raw materials of the hydroxyl-terminated Urethane Prepolymer (UPH). Further, it is preferable that the pot life and initial hardenability are improved by using an active hydrogen group-containing compound (HB) containing a primary hydroxyl group having an appropriate reactivity.
If the pot life of the adhesive is good, the viscosity of the adhesive does not become too high until the adhesive is applied to the base sheet, and uniform application of the adhesive can be achieved. When the initial hardenability of the adhesive is good, the coating layer or the adhesive layer is less likely to be affected by hot air during heating and drying of the coating layer or mechanical stress applied during winding and curing of the adhesive sheet obtained after heating and drying, and the occurrence of surface appearance defects such as core step marks, orange peel defects, and curling in the adhesive layer can be suppressed.
In addition to the above effects, the wettability-improving effect of the adhesive layer can be obtained by using a polyol (HA) having a relatively high molecular weight as one of raw materials of the hydroxyl-terminated Urethane Prepolymer (UPH). Further, by using the active hydrogen group-containing compound (HB) having a relatively low molecular weight as one of the raw materials of the hydroxyl-terminated Urethane Prepolymer (UPH), the effect of improving the removability of the adhesive layer can be obtained.
When the adhesive layer has good wettability, bubbles can be prevented from being caught in the adhesion interface when the adhesive sheet is adhered to an adherend such as glass. If the pressure-sensitive adhesive layer has good removability, contamination of the adherend, in which the adhesive component remains on the surface of the adherend after the removability of the pressure-sensitive adhesive sheet, can be effectively suppressed.
[ use ]
The adhesive sheet of the present invention can be used in the form of a tape, a label, a sheet, a double-sided tape, or the like. The adhesive sheet of the present invention can be preferably used as a surface protective sheet, a cosmetic sheet, an anti-slip sheet, and the like.
Flat panel displays such as Liquid Crystal Displays (LCDs) and organic electroluminescent displays (OELDs), and touch panel displays in which the flat panel displays and the touch panel are combined are widely used in electronic devices such as Televisions (TVs), Personal Computers (PCs), mobile phones, and portable information terminals.
The adhesive sheet of the present invention can be preferably used as a surface protective sheet for flat panel displays, touch panel displays (these are also collectively referred to simply as "displays"), substrates produced or used in the production steps thereof (glass substrates, and Indium Tin Oxide (ITO)/glass substrates having an ITO film formed on a glass substrate, etc.), optical members, and the like.
[ examples ]
Production examples, examples of the present invention, and comparative examples are described below. In the following description, "part" means part by mass, "%" means% by mass, and "RH" means relative humidity unless otherwise specified.
[ evaluation items and evaluation methods ]
The evaluation items and evaluation methods are as follows.
(Mn、Mw)
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the urethane prepolymer were measured by a Gel Permeation Chromatography (GPC) method. The measurement conditions were as follows. Both Mn and Mw are values in terms of polystyrene.
< measurement conditions >
The device comprises the following steps: shimadzu excellence (Shimadzu project) (manufactured by Shimadzu corporation),
Pipe column: two TSKgel GMHs manufactured by Tosoh (TOSOH) are connected in series,
A detector: a differential refractive index detector (RID-10A),
Solvent: tetrahydrofuran (THF),
Flow rate: 1mL/min,
Temperature of the solvent: at 40 deg.C,
Sample concentration: 0.1 percent,
Sample injection amount: 100 μ L.
(viscosity at 25 ℃ C.)
The viscosity of the urethane prepolymer-containing solution, the polyol-containing solution, and the adhesive at 25 ℃ was measured by placing a sample in a glass bottle with a lid, immersing the glass bottle in a constant-temperature water bath at 25 ℃ and taking out the glass bottle after a predetermined time, and then using a type B viscometer ("TVB 10 type viscometer" manufactured by eastern industries).
The urethane prepolymer-containing solution and the polyol-containing solution were placed in a glass bottle with a cap immediately after the preparation, and were immersed in a water bath at a constant temperature of 25 ℃ for 1 hour, after which the viscosity measurement was performed.
The adhesive was put into a glass bottle with a cap immediately after the preparation, and the glass bottle was immersed in a constant temperature water bath at 25 ℃ for 3 hours before the measurement. The viscosity shortly after 3 hours after preparation is assumed to be "viscosity at the application time point".
In the actual method for producing the adhesive sheet, the time from immediately after the preparation of the self-adhesive agent to the application thereof is not particularly limited, but is preferably within 6 hours, more preferably within 3 hours, from the viewpoint of optimizing the viscosity of the adhesive at the time of application.
(concentration of solid component)
The solid content concentrations of the urethane prepolymer-containing solution, the polyol-containing solution, and the adhesive were determined from the change in mass after drying relative to that before drying after heating and drying about 1g of the sample at 120 ℃ for 20 minutes.
(VOC reducing effect of adhesive)
The solid content concentration of the adhesive was measured by the method described above, and the VOC reducing effect of the adhesive was evaluated. The higher the solid content concentration is, the smaller the amount of the organic solvent used becomes, and the higher the effect of reducing Volatile Organic Compounds (VOC) can be said to be. The evaluation criteria are as follows.
Very good: the solid content concentration is preferably 90 mass% or more.
O: the solid content concentration is preferably 80 mass% or more and less than 90 mass%.
And (delta): the solid content concentration is 70 mass% or more and less than 80 mass%, and is practical.
X: the solid content concentration is less than 70% by mass, and therefore, the method cannot be practically used.
(pot life)
The adhesive immediately after the preparation was put into a glass bottle with a cap, the glass bottle was immersed in a constant temperature water bath at 25 ℃, and the viscosity was measured 1 hour after the start of immersion and 6 hours after the start of immersion, respectively. The rate of increase in viscosity after 6 hours from that after 1 hour (viscosity after 6 hours/viscosity after 1 hour [ times ]) was determined. The evaluation criteria are as follows.
Very good: the viscosity increase rate was less than 200%, and the product was excellent.
O: the viscosity increase rate was 200% or more and less than 300%, which was good.
And (delta): the viscosity increase rate is more than 300% and less than 400%, and is practical.
X: the viscosity increase rate was 400% or more, and it was not practical.
(initial hardenability)
In each of examples 1 to 54 and comparative examples 1 to 4, a sample (3-hour curing adhesive sheet) cured for 3 hours in an environment of 23 to 50% RH and a sample (120-hour curing adhesive sheet) cured for 120 hours in an environment of 23 to 50% RH were prepared for the adhesive sheet obtained by applying an adhesive to a base sheet and drying the adhesive sheet.
For each sample, the gel fraction (% by mass) was calculated as follows.
A test piece having a width of 30mm and a length of 100mm was cut out from the adhesive sheet after curing for a predetermined time, and attached to an SUS net (pore diameter: 0.077mm, wire diameter: 0.05 mm). This was immersed in ethyl acetate, extracted at 50 ℃ for 24 hours, and then dried at 100 ℃ for 30 minutes, and the gel fraction (% by mass) was calculated based on the following formula (1).
Gel fraction (% by mass) was (G2/G1) × 100. (1)
In the formula, each symbol represents the following parameter.
G1: the quality of the adhesive layer before extraction was carried out with ethyl acetate,
g2: the quality of the adhesive layer after extraction with ethyl acetate and drying was used.
Further, the rate of change in gel fraction during 3 hours of curing and 120 hours of curing was calculated based on the following formula (2).
Gel fraction change (%) (H1/H2) × 100. (2)
In the formula, each symbol represents the following parameter.
H1: gel fraction of the adhesive layer of the adhesive sheet cured for 3 hours,
h2: gel fraction of the adhesive layer of the adhesive sheet cured for 120 hours.
The evaluation criteria are as follows.
O: the gel fraction change rate was as good as 70% or more.
And (delta): the gel fraction change rate is 30% or more and less than 70%, and is practical.
X: the gel fraction change rate was less than 30%, and the method was not practical.
(wettability)
In each of examples 1 to 54 and comparative examples 1 to 4, an adhesive sheet obtained by applying an adhesive to a base sheet and drying the adhesive sheet was cured for 120 hours in an environment of 23 to 50% RH, a test piece having a width of 50mm and a length of 100mm was cut out from the adhesive sheet, and a release sheet was released from the test piece after leaving the adhesive sheet in an environment of 23 to 50% RH for 30 minutes. One end of the test piece from which the release sheet was peeled in the longitudinal direction was fixed to the end of the glass plate, and the other end, which was not fixed, was lifted up by hand from the surface of the glass plate to a position of 5cm in height. In this state, the hand was released, and the time taken until the entire adhesive layer (length 100mm) was closely adhered to the surface of the glass plate was measured. The evaluation criteria are as follows.
O: the time until the entire adhesive layer was adhered was preferably less than 3 seconds.
And (delta): the time until the entire adhesive layer is sealed is 3 seconds or more and less than 6 seconds, and this is practical.
X: the time taken until the entire adhesive layer is sealed is 6 seconds or more, and therefore, it is not practical.
(removability)
In each of examples 1 to 54 and comparative examples 1 to 4, an adhesive sheet obtained by applying an adhesive to a base sheet and drying the adhesive sheet was cured in an atmosphere of 23 to 50% RH for 120 hours, and then two test pieces having a width of 70mm and a length of 100mm were cut out from the adhesive sheet. For the two test pieces, the release sheet was peeled off in an environment of 23 to 50% RH, and a sodium hydroxide glass plate was attached to the surface of the exposed adhesive layer, followed by pressure bonding using a laminator. The two laminates thus obtained were placed in an oven set at 60 ℃ to 90% RH for 72 hours (condition 1) and 120 hours (condition 2), respectively. After heating in an oven for a predetermined time, the two laminates were taken out, air-cooled in an environment of 23 to 50% RH for 3 hours, and then the adhesive sheet was peeled from the glass plate, and the removability was evaluated by visual observation. The evaluation criteria are as follows.
O: under all conditions, no adhesive layer component was attached to the glass surface, and the adhesion was excellent.
And (delta): in condition 1, no adhesive layer component was attached to the glass surface at all, but in condition 2, adhesive layer component was attached to the glass surface, and it was found to be practical.
X: under all conditions, the adhesion layer component was adhered to the glass surface, and it was not practical.
[ Material ]
The materials used are as follows.
< polyol (HA) having number average molecular weight (Mn) of 1000 or more >
(HA-1): p-1010 (abbreviated as P-1010 in the table), a bifunctional polyester polyol manufactured by Kuraray, Mn 1000, hydroxyl number 2, hydroxyl number 112, a polyol having a hydroxyl value of,
(HA-2): (iii) a polyol F-3010 (abbreviated as F-3010 in the table), a trifunctional polyester polyol manufactured by Koraray, Mn of 3000, hydroxyl number of 3, hydroxyl number of 56, a polyol prepared by Koraray,
(HA-3): PEG-1000, a difunctional polyether polyol (polyethylene glycol) manufactured by Sanyo chemical Co., Ltd., Mn of 1000, hydroxyl number of 2, hydroxyl value of 112,
(HA-4): poly bd, a difunctional polyolefin polyol manufactured by Shikino corporation, Mn 2800, hydroxyl number 2, hydroxyl value 40,
(HA-5): PP-2000, a difunctional polyether polyol manufactured by Sanyo chemical Co., Ltd., Mn 2000, hydroxyl number 2, hydroxyl value 56,
(HA-6): excenol 5030 (abbreviated as EXCE5030 in the table), a trifunctional polyether polyol manufactured by Asahi glass company, Mn 5100, hydroxyl number 3, hydroxyl value 33,
(HA-7): acrosso (Excenol)851 (abbreviation: EXCE851 in the table), manufactured by Asahi glass company, trifunctional polyether polyol, Mn 6700, hydroxyl number 3, hydroxyl number 25.
(HA-8): preminol S4013F (abbreviation: PREM S4013F in the table), a difunctional polyether polyol manufactured by Asahi glass company, Mn 12000, hydroxyl number 2, hydroxyl number 9,
(HA-9): preminol S3011 (abbreviation: PREM S3011 in the table), a trifunctional polyether polyol manufactured by Asahi glass company, Mn 10000, hydroxyl number 3, and hydroxyl number 17.
< active hydrogen group-containing Compound (HB) having a number average molecular weight (Mn) of less than 1000 >
(HB-1): ethylene Glycol (EG), a compound containing only primary hydroxyl groups,
(HB-2): 1, 5-pentanediol, a monomer containing only primary hydroxyl groups,
(HB-3): 2-ethyl-1, 3-hexanediol (also known as 1, 3-octanediol), a polymer containing a primary hydroxyl group and a secondary hydroxyl group,
(HB-4): PPG200 (the number indicates Mn, and the same applies to PEG), polypropylene glycol, a polymer produced by Sanyo chemical Co., Ltd., containing only a secondary hydroxyl group,
(HB-5): PEG300, polyethylene glycol, a compound containing only a primary hydroxyl group, a compound produced by Sanyo chemical Co., Ltd,
(HB-6): PEG600, polyethylene glycol, a compound containing only a primary hydroxyl group, manufactured by Sanyo chemical Co Ltd,
(HB-7): glycerol, a compound containing a primary hydroxyl group and a secondary hydroxyl group,
(HB-8): trimethylolpropane (TMP), a polymer containing only primary hydroxyl groups,
(HB-9): 1-methylamino-2, 3-propanediol (MAPD), a trifunctional amino group-containing polyol made by Tokyo chemical industries, Mn 105, containing a primary hydroxyl group, a secondary hydroxyl group, and an amino group.
< polyisocyanate (N) >
(N-1): isophorone diisocyanate (IPDI), manufactured by Tokyo chemical industries, Inc,
(N-2): hexamethylene Diisocyanate (HDI), manufactured by Tokyo chemical industries, Ltd,
(N-3): tolylene diisocyanate (a mixture of 2, 4-tolylene diisocyanate (80 mass%) and 2, 6-tolylene diisocyanate (20 mass%) (TDI), manufactured by Tosoh corporation.
< organic solvent (B) >
(B-1): ethyl acetate and cellosolve (Daicel).
< plasticizer (P) >
(P-1): maleic acid ester plasticizer, dioctyl maleate (DOM), manufactured by Daihachi chemical Co., Ltd,
(P-2): orthophosphoric acid ester plasticizer, tris (2-ethylhexyl) phosphate (TOP), available from Daihachi chemical Co., Ltd,
(P-3): polyether ester plasticizer, RS-700, Adeca (ADEKA).
< antioxidant (D) >
(D-1): yillonus (IRGANOX)1135, manufactured by BASF corporation.
< beta-diketone compound (X) (hardening retarder) >
(X-1): acetylacetone, manufactured by tokyo chemical industries co.
< antistatic agent (AS agent) (F) >
(F-1): elekcel (Elexcel) AS-804, first Industrial pharmaceutical company.
< polyfunctional isocyanate Compound (I) >
(I-1): sumido (Sumidur) N-3300 manufactured by Sumika Bayer Urethane, Hexamethylene Diisocyanate (HDI)/isocyanurate, 100 mass% of solid content,
(I-2): crotonate (Coronate) HL, manufactured by Tosoh corporation, Hexamethylene Diisocyanate (HDI)/Trimethylolpropane (TMP) adduct, 75% by mass of a solid content,
(I-3): desmodur (Desmodur) Z4470BA, manufactured by SumikaBayer Urethane, isophorone diisocyanate (IPDI)/isocyanurate, and a solid content of 70 mass%.
[ production of urethane prepolymer-containing solution or polyol-containing solution ]
Production example 1 (two-stage polymerization method)
100 parts by mass of polyol (HA-1), 40 parts by mass of polyisocyanate (N-1), 10 parts by mass of organic solvent (B-1) as a diluent, 100 parts by mass of plasticizer (P-1), and 0.01 part by mass of dioctyltin dilaurate as a catalyst were charged into a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, thermometer, and dropping funnel, and mixed. The content liquid was slowly heated to 80 ℃ and reacted for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (first-stage reaction). Then, the content liquid was cooled to 60 ℃ and 20 parts by mass of the active hydrogen group-containing compound (HB-2) were added and mixed to react (reaction in the second stage).
In the whole of the reactions in the first and second stages, the ratio (NCO/H) of the number of moles of isocyanate groups (NCO) in the polyisocyanate (N) used in the reaction to the total number of moles of active hydrogen groups (H) in all the active hydrogen group-containing compounds (HX) (in the above example, (HA-1) and (HB-2)) used in the reaction was 0.62.
After confirming the disappearance of the remaining isocyanate groups by infrared spectroscopy (infrared radiation, IR) analysis), the content liquid was cooled to complete the reaction, and then 1 part by mass of an antioxidant (D-1) and 3 parts by mass of a β -diketone compound (X-1) were added and mixed.
As described above, a colorless and transparent solution of the hydroxyl group-containing terminal urethane prepolymer (UPH-1) was obtained.
The main production conditions and evaluation results are shown in tables 1-1 and 2-1.
Tables 1-1 to 1-7 show the raw material composition, NCO/H, Mn and Mw of the urethane prepolymer alone or the polyol mixture alone.
Tables 2-1 to 2-2 show the composition of the urethane prepolymer-containing solution or the polyol-containing solution, the solid content concentration, and the viscosity at 25 ℃ immediately after the preparation after standing at 25 ℃ for 1 hour.
The unit of the amount of blending in the table is "part by mass" (the same applies to the other tables).
Production examples 2 to 40 and 42 to 45 (two-stage polymerization method)
Solutions of the hydroxyl group-containing terminal urethane prepolymers (UPH-2) to (UPH-45) were obtained by a two-stage polymerization method in the same manner as in production example 1, except that the kinds and blending ratios of the raw materials used were changed.
100 parts by mass of one or more polyols (HA) or one or more polyols (HL), one or more polyisocyanates (N), an organic solvent (B) and/or a plasticizer (P) as a diluent, and 0.01 part by mass of dioctyltin dilaurate as a catalyst were charged into a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel, and mixed. The content liquid was slowly heated to 80 ℃ and reacted for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (first-stage reaction). Then, the content liquid is cooled to 60 ℃, and one or more active hydrogen group-containing compounds (HB) are added and mixed to react (reaction in the second stage).
After confirming the disappearance of the remaining isocyanate group by infrared spectroscopic analysis (IR analysis), the content liquid was cooled to complete the reaction, and then antioxidant (D-1) and β -diketone compound (X-1) were added and optionally AS agent (F-1) was added and mixed. As described above, colorless and transparent solutions of the hydroxyl group-containing terminal urethane prepolymers (UPH-2) to (UPH-32), (UPH-34) and (UPH-37) were obtained.
The main production conditions and evaluation results are shown in tables 1-1 to 1-6 and tables 2-1 to 2-2.
Production example 41 (two-stage polymerization method)
A solution of a hydroxyl group-containing terminal urethane prepolymer (UPH-33) was obtained by a two-stage polymerization method in the same manner as in production example 1, except that the kind and blending ratio of the raw materials used were changed.
100 parts by mass of polyol (HB-6), 80 parts by mass of polyisocyanate (N-1), 10 parts by mass of organic solvent (B-1) and 100 parts by mass of plasticizer (P-1) as diluents, and 0.01 part by mass of dioctyltin dilaurate as catalyst were charged into a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, thermometer, and dropping funnel, and mixed. The content liquid was slowly heated to 80 ℃ and reacted for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (first-stage reaction). Then, the content liquid was cooled to 60 ℃, and the active hydrogen group-containing compound (HB-2) was added and mixed to react (second-stage reaction).
After confirming the disappearance of the remaining isocyanate group by infrared spectroscopic analysis (IR analysis), the content liquid was cooled to complete the reaction, and then an antioxidant (D-1) and a β -diketone compound (X-1) were added and mixed. A colorless and transparent solution of the hydroxyl group-containing terminal urethane prepolymer (UPH-41) was obtained as described above.
The main production conditions and evaluation results are shown in tables 1 to 6 and tables 2 to 2.
Production example 46 (one-stage polymerization method)
100 parts by mass of polyol (HA-6), 8 parts by mass of active hydrogen group-containing compound (HB-2), 10 parts by mass of organic solvent (B-1) as a diluent, 100 parts by mass of plasticizer (P-1), and 0.01 part by mass of dioctyltin dilaurate as a catalyst were charged into a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet, thermometer, and dropping funnel, and mixed, and the content liquid was gradually heated to 80 ℃. Then, 13 parts by mass of polyisocyanate (N-1) was added and the reaction was carried out for 2 hours. After confirming the disappearance of the remaining isocyanate group by infrared spectroscopic analysis (IR analysis), the content liquid was cooled to complete the reaction, and 1 part by mass of an antioxidant (D-1) and 3 parts by mass of a β -diketone compound (X-1) were added and mixed. A colorless and transparent solution of the hydroxyl group-containing terminal urethane prepolymer (UPH-38) was obtained as described above.
The main production conditions and evaluation results are shown in tables 1 to 6 and tables 2 to 2.
Production examples 47 and 48 (one-stage polymerization method)
A four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel was charged with and mixed with 30 parts by mass of polyol (HA-1), 70 parts by mass of polyol (HA-7), 5 parts by mass of polyisocyanate (N-2), 90 parts by mass or 30 parts by mass of organic solvent (B-1) as a diluent, 40 parts by mass of plasticizer (P-1), and 0.01 part by mass of dioctyltin dilaurate as a catalyst. The content liquid was slowly heated to 80 ℃ and reacted for 2 hours.
After confirming the disappearance of the remaining isocyanate group by infrared spectroscopic analysis (IR analysis), the content liquid was cooled to complete the reaction, and 1 part by mass of an antioxidant (D-1) and 3 parts by mass of a β -diketone compound (X-1) were added and mixed. As described above, a colorless and transparent solution of the hydroxyl group-containing terminal urethane prepolymer for comparison (UPH-39) was obtained.
The main production conditions and evaluation results are shown in tables 1 to 7 and tables 2 to 2.
Production example 49 (one-stage polymerization method)
100 parts by mass of a polyol (HA-6), 5 parts by mass of an active hydrogen group-containing compound (HB-2), 40 parts by mass of a polyisocyanate (N-1), 10 parts by mass of an organic solvent (B-1) as a diluent, 100 parts by mass of a plasticizer (P-1), and 0.01 part by mass of dioctyltin dilaurate as a catalyst were charged into a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, a thermometer, and a dropping funnel, and mixed. The content liquid was slowly heated to 80 ℃ and reacted for 2 hours.
After the reaction was completed by cooling the content liquid, 1 part by mass of an antioxidant (D-1) and 3 parts by mass of a beta-diketone compound (X-1) were added and mixed. As described above, a colorless and transparent solution of the isocyanate group-containing terminal urethane prepolymer (UPN-1) for comparison was obtained.
The main production conditions and evaluation results are shown in tables 1 to 7 and tables 2 to 2.
Production example 50
A colorless and transparent comparative polyol (PO-1) -containing solution was obtained by mixing 100 parts by mass of polyol (HA-6), 5 parts by mass of active hydrogen group-containing compound (HB-2), 10 parts by mass of organic solvent (B-1) as a diluent, 100 parts by mass of plasticizer (P-1), 0.01 part by mass of dioctyltin dilaurate as a catalyst, 1 part by mass of antioxidant (D-1), and 3 parts by mass of beta-diketone compound (X-1).
The main production conditions and evaluation results are shown in tables 1 to 7 and tables 2 to 2.
[ production of urethane adhesive and adhesive sheet ]
(examples 1 to 54 and comparative examples 1 to 4)
The urethane-based adhesive is obtained by mixing the urethane prepolymer-containing solution or the polyol-containing solution obtained in any one of the production examples, the polyfunctional isocyanate compound (I), and an optional organic solvent (B) and stirring the mixture with a dispersing machine.
The obtained adhesive was evaluated for the solid content concentration, the viscosity immediately after preparation and after standing at 25 ℃ for 3 hours, and the pot life.
A50 μm-thick polyethylene terephthalate (PET) film (Lumiler T-60, manufactured by Toray corporation) was prepared as a substrate sheet. A urethane adhesive which was allowed to stand at 25 ℃ for 3 hours or less after the preparation was applied to one surface of the substrate sheet using a chipped-wheel coater (registered trademark) so that the thickness after drying became 12 μm. Then, the formed coating layer was dried at 100 ℃ for two minutes to form a coherent layer. A release sheet (Super Stik) SP-PET38, manufactured by Lintec, Inc. was attached to the adhesive layer to a thickness of 38 μm to obtain an adhesive sheet. After curing for a predetermined time under the condition of 23 to 50% RH, initial curability, wettability, and removability were evaluated. In addition, comparative example 4 is an example in which an adhesive was produced by a single process.
The formulation composition of the adhesive and the evaluation results of the adhesive and the adhesive sheet are shown in tables 3-1 to 3-2 and tables 4-1 to 4-2.
[ evaluation results ]
Production examples 1 to 46 are solutions of hydroxyl-terminal Urethane Prepolymer (UPH) which is a reaction product of one or more active hydrogen group-containing compounds (HX) and one or more polyisocyanates (N), and which has a solid content concentration of 80 mass% or more and a viscosity of 8000mPa · s or less at 25 ℃ immediately after production after standing at 25 ℃ for 1 hour. In all of these production examples, solutions of hydroxyl group-containing terminal urethane prepolymers having a reduced amount of organic solvent used, a relatively high solid content concentration and a relatively low viscosity were synthesized.
In examples 1 to 54, an adhesive comprising the solution of the hydroxyl group-containing terminal urethane prepolymer obtained in any one of production examples 1 to 46 and the polyfunctional isocyanate compound (I) and having a solid content concentration of 70% by mass or more or 80% by mass or more was prepared, and the viscosity at 25 ℃ immediately after the preparation was left to stand at 25 ℃ for 3 hours was 9000mPa · s or 5000mPa · s or less. In these examples, an adhesive sheet was produced using an adhesive that was left to stand at 25 ℃ for 3 hours or less immediately after the preparation. In any of the examples, the applicability of the adhesive was good.
In each of examples 1 to 54, an adhesive having a reduced amount of an organic solvent used, a relatively high solid content concentration, and a relatively low viscosity at the time of application to provide good applicability to application was produced. In any of these examples, an adhesive having a good pot life and an adhesive sheet having good initial curability, wettability and removability can be produced.
The solution of the hydroxyl group-containing terminal urethane prepolymer obtained in production example 47 had a low solid content concentration, and the adhesive of comparative example 1 using this had a low solid content concentration, and the VOC reducing effect was not good.
The solution of the hydroxyl group-containing terminal urethane prepolymer obtained in production example 48 had a high viscosity, and the adhesive of comparative example 2 using the same had a high viscosity, a poor pot life, and a poor coatability.
The adhesive of comparative example 3 using the solution containing the isocyanate group-terminated urethane prepolymer obtained in production example 49 had a poor pot life, and the adhesive sheet using the same had a poor initial curability.
The adhesive was produced by a single process using the polyol-containing solution obtained in production example 50 in comparative example 4. The adhesive sheet using the adhesive has poor initial curability.
[ tables 1-1]
Figure BDA0003310345040000271
Figure BDA0003310345040000281
Figure BDA0003310345040000291
Figure BDA0003310345040000301
Figure BDA0003310345040000311
Figure BDA0003310345040000321
Figure BDA0003310345040000331
Figure BDA0003310345040000341
Figure BDA0003310345040000351
Figure BDA0003310345040000361
Figure BDA0003310345040000371
[ Table 4-1]
Figure BDA0003310345040000381
[ tables 4-2]
Figure BDA0003310345040000391
The present invention is not limited to the above-described embodiments and examples, and design changes can be made as appropriate without departing from the spirit of the present invention.
The present application claims priority based on japanese patent application No. 2019-.
Description of the symbols
10. 20: adhesive sheet
11. 21: substrate sheet
12. 22A, 22B: adhesive layer
13. 23A, 23B: release sheet

Claims (16)

1. A solution of a hydroxyl-terminated urethane prepolymer for an adhesive, the solution of the hydroxyl-terminated urethane prepolymer comprising a hydroxyl-terminated Urethane Prepolymer (UPH) which is a reaction product of one or more active hydrogen group-containing compounds (HX) having a plurality of active hydrogen groups in one molecule and one or more polyisocyanates (N), and
the solid content concentration is 80 mass% or more, and the viscosity at 25 ℃ after standing still at 25 ℃ for 1 hour immediately after the preparation is 8000 mPas or less.
2. The solution of hydroxyl-terminated urethane prepolymer according to claim 1, wherein the one or more active hydrogen group-containing compounds (HX) comprise one or more polyols (HA) having a number average molecular weight of 1000 or more and one or more active hydrogen group-containing compounds (HB) having a number average molecular weight of less than 1000 and having a plurality of active hydrogen groups in one molecule.
3. The solution containing a hydroxyl terminated urethane prepolymer according to claim 1 or 2, wherein one or more polyols (HA) comprise trifunctional or higher polyether polyols.
4. The solution of hydroxyl-terminated urethane prepolymer according to any one of claims 1 to 3, wherein the ratio (NCO/H) of the number of moles of isocyanate groups (NCO) of one or more polyisocyanates (N) to the total number of moles of active hydrogen groups (H) of one or more active hydrogen group-containing compounds (HX) is 0.20 to 0.84.
5. The solution of hydroxyl-terminal urethane prepolymer in accordance with any one of claims 1 to 4, wherein the hydroxyl-terminal Urethane Prepolymer (UPH) is a reaction product of an isocyanate-group-terminal Urethane Prepolymer (UPN) which is a reaction product of a polyol (HA) and a polyisocyanate (N), and an active hydrogen group-containing compound (HB).
6. The solution of hydroxyl-terminated urethane prepolymer according to any one of claims 1 to 5, wherein one or more polyisocyanates (N) comprise isophorone diisocyanate.
7. The solution of the hydroxyl-terminated urethane prepolymer according to any one of claims 1 to 6, wherein the active hydrogen group-containing compound (HB) contains a primary hydroxyl group.
8. An adhesive comprising a solution of the hydroxyl-containing terminal urethane prepolymer according to any one of claims 1 to 7, and a polyfunctional isocyanate compound (I).
9. The adhesive according to claim 8, wherein the solid content concentration is 80% by mass or more, and the viscosity at 25 ℃ immediately after the preparation is left to stand at 25 ℃ for 3 hours is 5000 mPas or less.
10. The adhesive of claim 8 or 9, further comprising a plasticizer.
11. The adhesive of any one of claims 8 to 10, further comprising a beta diketone compound.
12. The adhesive of any one of claims 8 to 11, further comprising an antistatic agent.
13. The adhesive according to any one of claims 8 to 12, further comprising one or more deterioration preventing agents selected from the group consisting of an antioxidant, a hydrolysis resistance agent, an ultraviolet absorber, and a light stabilizer.
14. An adhesive sheet comprising a substrate sheet and an adhesive layer containing a cured product of the adhesive according to any one of claims 8 to 13.
15. A method for producing a solution containing a hydroxyl-terminated urethane prepolymer according to claim 2, the method comprising:
a step of reacting one or more polyols (HA) having a number average molecular weight of 1000 or more with one or more polyisocyanates (N) at an excess isocyanate group ratio to produce an isocyanate group-terminated Urethane Prepolymer (UPN); and
a step of reacting the isocyanate group-terminated Urethane Prepolymer (UPN) thus obtained with one or more active hydrogen group-containing compounds (HB) having a number average molecular weight of less than 1000 and a plurality of active hydrogen groups in one molecule.
16. A method for producing an adhesive sheet according to claim 14, comprising:
a step of mixing at least the solution of the hydroxyl group-containing terminal urethane prepolymer with a polyfunctional isocyanate compound (I) to prepare an adhesive having a solid content concentration of 80 mass% or more;
a step of applying the adhesive to the base sheet to form a coating layer; and
a step of drying the coating layer,
the adhesive has a viscosity of 5000 mPas or less at 25 ℃ at the time of application.
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