CN104955913A - Adhesive composition, and laminate and method for manufacturing same - Google Patents

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

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Publication number
CN104955913A
CN104955913A CN201480005475.8A CN201480005475A CN104955913A CN 104955913 A CN104955913 A CN 104955913A CN 201480005475 A CN201480005475 A CN 201480005475A CN 104955913 A CN104955913 A CN 104955913A
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CN
China
Prior art keywords
adhesive composition
glycol
diphenylmethanediisocyanate
mole
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201480005475.8A
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Chinese (zh)
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CN104955913B (en
Inventor
宇佐勇贵
内山裕清
佐藤义浩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyo Morton Ltd
Toyochem Co Ltd
Artience Co Ltd
Original Assignee
Toyo Morton Ltd
Toyo Ink SC Holdings Co Ltd
Toyochem Co Ltd
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Publication of CN104955913A publication Critical patent/CN104955913A/en
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Publication of CN104955913B publication Critical patent/CN104955913B/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

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

Description

Adhesive composition and duplexer and manufacture method thereof
Technical field
The present invention relates to a kind of adhesive composition.And relate to a kind of duplexer and the manufacture method thereof that use above-mentioned adhesive composition.
Background technology
The laminating each other of various plastic film or the laminating of plastic film and metal deposition film or tinsel, former, undertaken by the dry type laminar way of the solvent based cement using hydroxyl/isocyanate system.But dry type laminar way, owing to using containing the solid of organic solvent, therefore needs to suppress, prevents the pollution of the environment or the special equipment of fire.
In recent years, due to the requirement to easy equipment, and the requirement of the de-organic solvent of solid is strengthened, and carry out the research of solvent free energetically.
Such as, disclose in patent documentation 1: containing polyhydroxy reactant (1) and the solventless laminating adhesive composition of polisocyanate component (2) comprising two kinds of polyisocyanate compounds.
In addition, disclose in patent documentation 2: can the polisocyanate component (2) of polyisocyanate compounds, branching point concentration be specified range, hydroxyl moles containing polyhydroxy reactant (1) with 3 officials must be had: isocyanate group mole number=1: the solventless laminating adhesive composition of 1 ~ 1: 3.
Disclose in patent documentation 3: containing polyhydroxy reactant (A) and the no-solvent type adhesive composition of isocyanate prepolymer composition (B) must with isophorone diisocyanate.
Disclose in patent documentation 4: the no-solvent type adhesive composition of the confused body (C) containing polyhydroxy reactant (A) and polyisocyanate compounds (B) and specified particle diameter.
And disclose in patent documentation 5: containing polisocyanate component (a) and polyhydroxy reactant (b), and polisocyanate component (a) comprises single mass system 4, the adhesive composition of 4 '-methylenediphenyl diisocyanates (i) and isocyanate-functional's prepolymer (ii).Isocyanate-functional's prepolymer (ii) comprises single mass system 4,4 '-methylenediphenyl diisocyanates, reaction product with the prepolymer reactive material mixture of more than one polyvalent alcohols, as more than one polyvalent alcohol, specify and comprise the triol with the molecular-weight average being in specified range.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 8-60131 publication
Patent documentation 2: Japanese Patent Laid-Open 2003-96428 publication
Patent documentation 3: Japanese Patent Laid-Open 2006-57089 publication
Patent documentation 4: Japanese Patent Laid-Open 2011-162579 publication
Patent documentation 5: Japanese Patent Laid-Open 2012-131980 publication
Summary of the invention
The problem that invention will solve
As the method using adhesive composition to obtain duplexer, normally after base material (object then) upper coating adhesive composition, under the state of other base materials (object then) overlapping in formed adhesion agent layer, carry out the method for the sclerosis of the adhesion agent layer clamped by two base materials.Below, above-mentioned " carrying out the sclerosis of adhesion agent layer " step is called " Aging Step ".
Invention described in patent documentation 1 ~ patent documentation 4, specifically uses alicyclic ring family polisocyanate component or fatty family polisocyanate component as polisocyanate component.Alicyclic ring family polisocyanate component or fatty family polisocyanate component are due to reaction relatively gentleness, and therefore Aging Step needs to carry out 2 days ~ 5 days at 40 DEG C ~ 50 DEG C.But in the market, requiring to provide can be aging and show the adhesive composition of equal above then performance with the time short than before.
Compared with alicyclic ring family polisocyanate component or fatty family polisocyanate component, because fragrant family polisocyanate component is rich reactive, therefore consistent with the problem of the short period of time of digestion time.But, because fragrant family polisocyanate component is rich reactive, therefore with the reaction of polyhydroxy reactant with compete with the reaction of the water in ambient moisture, in order to show sufficient adhesion, and need ambient moisture when applying, time overlapping and time aging strictly to manage as low humidity.Therefore, in the market, even if require to provide and ambient moisture is not strictly managed into low humidity, also can be aging and show the adhesive composition of equal above then performance with the time short than before.
Invention described in patent documentation 5 can show then performance with the aging of relatively short period of time, but after polyhydroxy reactant mixes with polisocyanate component, is present in viscosity in the short period of time and extremely increases, the problem namely shortened the working life of adhesive composition.
The present invention is in view of above-mentioned background forms, even if its objective is that providing a kind of does not strictly manage ambient moisture as low humidity, also can be aging and show equal above then performance with the time short than before, and working life long adhesive composition and use duplexer and the manufacture method thereof of above-mentioned adhesive composition.
The technique means of dealing with problems
The present invention forms in view of above-mentioned problem, as polisocyanate component (A), contains the polisocyanate component derived by two kinds of fragrant family isocyanic ester and polyether glycol; As polyhydroxy reactant (B), the polyhydroxy reactant containing the polyester glycol and relatively low low-molecular-weight glycol or triol that comprise specified molecular weight.
Namely, the present invention relates to a kind of adhesive composition, it comprises polisocyanate component (A) and polyhydroxy reactant (B), and above-mentioned polisocyanate component (A) makes to have 2, 4 '-diphenylmethanediisocyanate (a1) and 4, the isocyanic ester of 4 '-diphenylmethanediisocyanate (a2), with the polyvalent alcohol must with polyether glycol (a3), the reactive products of reacting under the condition that isocyanate group is excessive, above-mentioned polyhydroxy reactant (B) is that must to have number average molecular weight be more than 500, 3, the polyester glycol (b1) of less than 000, and to comprise number average molecular weight be more than 50, and be less than 500 glycol (b2) and number average molecular weight be more than 50, and be less than at least any one the polyhydric alcohol composition of the triol (b3) of 500.
Adhesive composition of the present invention is preferably, 2,4 '-diphenylmethanediisocyanate (a1) and 4, in 100 % by mole of the total of 4 '-diphenylmethanediisocyanate (a2), by 2,4 '-diphenylmethanediisocyanate (a1) is set to more than 10 % by mole, less than 60 % by mole, and 4,4 '-diphenylmethanediisocyanate (a2) is set to more than 40 % by mole, less than 90 % by mole.
In addition, adhesive composition of the present invention is preferably, in polyhydroxy reactant (B) 100 quality %, comprise more than polyester glycol (b1) 60 quality %, below 99 quality %, and more than total 1 quality %, below the 40 quality % of glycol (b2) and triol (b3).
In addition, be preferably when the hydroxyl moles in polyhydroxy reactant (B) is set to 100 moles, the mole number of the isocyanate group in polisocyanate component (A) is more than 70 moles, less than 300 moles.
In addition, adhesive composition of the present invention is preferably no-solvent type.
In addition, adhesive composition of the present invention is preferably the laminated solid of wrapping material formation.
And the present invention relates to a kind of duplexer, it uses to form as above-mentioned adhesive composition of the present invention carrys out stacked two flat substrates.
And, the present invention relates to a kind of manufacture method of duplexer, the adhesive composition of the invention described above is coated on the 1st flat substrates and forms adhesion agent layer by it, and in above-mentioned adhesion agent layer overlapping 2nd flat substrates, by the above-mentioned adhesion agent layer sclerosis between two flat substrates.
The effect of invention
According to the present invention, there is the effect of following excellence: strictly do not managed by ambient moisture as low humidity even if can provide, also can be aging and show equal above then performance with the time short than before, and working life long adhesive composition and use duplexer and the manufacture method thereof of above-mentioned adhesive composition.
Embodiment
Adhesive composition of the present invention comprises polisocyanate component (A) and polyhydroxy reactant (B).
Polisocyanate component (A) makes to have 2,4 '-diphenylmethanediisocyanate (2,4 '-diphenylmethane diisocyanate) (a1) and 4,4 '-diphenylmethanediisocyanate (4,4 '-diphenylmethane diisocyanate) (a2) isocyanic ester, with must have the polyvalent alcohol of polyether glycol (a3), the reactive products of reacting under the condition that isocyanate group is excessive.Below, also sometimes by 2,4 '-diphenylmethanediisocyanate (a1) referred to as 2,4 '-MDI (a1), by 4,4 '-diphenylmethanediisocyanate (a2) referred to as 4,4 '-MDI (a2).
Polyhydroxy reactant (B) is that must to have number average molecular weight be more than 500,3, the polyester glycol (b1) of less than 000, and comprise number average molecular weight be more than 50 and be less than 500 glycol (b2) and number average molecular weight be more than 50 and be less than at least any one the polyhydric alcohol composition of the triol (b3) of 500.
By above-mentioned formation, ambient moisture is not strictly managed into low humidity even if can provide, also can be aging and show equal above then performance with the time short than before, and the adhesive composition that working life is long.Adhesive composition of the present invention does not get rid of the solvent-laden situation of bag, but is excellent with regard to the aspect that yet can be applicable to no-solvent type.In addition, so-called no-solvent type is not solvent-laden in fact, and containing solvent inevitably residual in manufacturing step etc., maybe to the solvent of the trace that characteristic impacts, also can not be included in the present invention in no-solvent type.Below, the present invention is described in detail.
Polisocyanate component (A) comprises: by 2,4 '-MDI (a1) mixes with the carbamate prepolymer of polyol reaction and the carbamate prepolymer of 4,4 '-MDI (a2) and polyol reaction; And/or the carbamate prepolymer of 2,4 '-MDI (a1) and 4,4 '-MDI (a2) and polyol reaction.In addition, unreacted 2,4 '-MDI (a1) or unreacted 4,4 '-MDI (a2) can be comprised.
By 4,4 '-MDI (a2) and 2,4 '-MDI (a1) are used as polisocyanate component (A), even if the short period of time is aging, then performance also can be played fully.On the other hand, by by 2,4 '-MDI (a1) and 4,4 '-MDI (a2) and use, even if the coating under high humidity environment, overlap, aging, then performance also can be given play to fully.In addition, in 100 % by mole of the total of 2,4 '-MDI (a1) and 4,4 '-MDI (a2), be preferably 2,4 '-MDI (a1) and be set to 10 % by mole ~ 60 % by mole and (comprise higher limit and lower value.Identical below), 4,4 '-MDI (a2) are set to 40 % by mole ~ 90 % by mole.By the ratio of components of two kinds of MDI is set to above-mentioned scope, even and if ambient moisture is not strictly managed into low humidity, also can be aging and more effectively show equal above then performance with the time short than before.
The polyvalent alcohol forming polisocyanate component (A) is described.Polyvalent alcohol contains polyether glycol (a3) as essential component, can contain polyester polyol in addition.Polyether glycol is compared with polyester polyol, and the viscosity of usual molten state is low, and the polyvalent alcohol therefore when forming polisocyanate component (A) as the constituent of solid, importantly must have polyether glycol (a3).And, by also using polyester polyol, and the intermiscibility with aftermentioned polyhydroxy reactant (B) can be improved, and improve the cohesive force of adhesive composition.
When also using polyester polyol, with regard to the aspect of the viscosity of adhesive composition, in polyvalent alcohol 100 quality %, being preferably below 30 quality %, being more preferably 1 quality % ~ 30 quality %, be especially preferably 1 quality % ~ 20 quality %.
As polyether glycol (a3), include, for example: by low molecular weight polyols such as such as water, ethylene glycol, propylene glycol, TriMethylolPropane(TMP), glycerine as initiator, and the polyether glycol etc. that the epoxies such as oxyethane, propylene oxide, butylene oxide ring, tetrahydrofuran (THF) (oxirane) compound polymerization is obtained.
As polyether glycol (a3), except 2 officials can except, can use 3 officials can above.In addition, also multiple sense radix capable of being combined different and use.The number average molecular weight of polyether glycol (a3) is preferably more than 100,5, less than 000.In addition, also may be combined with the polyether glycol (a3) of multiple different quantities molecular-weight average and use.
As and polyester polyol, can enumerate: make the polyester polyol etc. that polycarboxylic acid composition and diol component react and obtain.
As polycarboxylic acid composition, include, for example: the polycarboxylic acids such as terephthalic acid, m-phthalic acid, hexanodioic acid, nonane diacid, sebacic acid or these dialkyl or these mixture.As diol component, include, for example: ethylene glycol, propylene glycol, Diethylene Glycol, butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, glycols or these the mixtures such as 5-pentanediol, 3,3-dihydroxymethyl heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether diol.
The present invention's polisocyanate component (A) used such as can make 2, the mixture of 4 '-MDI (a1) and 4,4 '-MDI (a2) and must have the polyol reaction of polyether glycol (a3) and obtain.Or, polisocyanate component (A) is also by making 2, the reaction product of gained respectively and must have the polyol reaction of polyether glycol (a3), and is obtained by mixing by 4 '-MDI (a1) and 4,4 '-MDI (a2).And polisocyanate component (A) is also by making 2, and 4 '-MDI (a1) and 4,4 '-MDI (a2) are sequentially and must have the polyol reaction of polyether glycol (a3) and obtain.
The polisocyanate component (A) that the present invention is used as long as make mentioned component react under the excessive condition of isocyanate group, to be preferably and to react in the scope of less than 6 more than 1 in the equivalence ratio of isocyanate group/hydroxyl, to be more preferably more than 1.5, react in the scope of less than 4.
By making 2 with the equivalence ratio of above-mentioned scope, 4 '-MDI (a1) and 4,4 '-MDI (a2) and polyol reactions, and the carbamate prepolymer of moderate amount molecular-weight average, the isocyanate group with moderate amount can be had.Its result for obtaining adhesive composition being mixed with aftermentioned polyhydroxy reactant (B) by polisocyanate component (A), and when using above-mentioned adhesive composition and obtain duplexer, can obtain sufficient Bonding strength.
Then, polyhydroxy reactant (B) used to the present invention is described.Polyhydroxy reactant (B) as described above, must have number average molecular weight is more than 500,3, the polyester glycol (b1) of less than 000, and comprise number average molecular weight be more than 50 and be less than 500 glycol (b2) or number average molecular weight be more than 50 and be less than the triol (b3) of 500 at least any one.The people such as the present inventor carry out active research repeatedly, and result is known, if be used alone polyester glycol (b1) as polyhydroxy reactant (B), then cannot obtain sufficient Bonding strength.In addition we know, if do not use polyester glycol (b1) and use glycol (b2) and/or triol (b3) as polyhydroxy reactant (B), then not only working life is short, and cannot obtain sufficient Bonding strength.Namely, find out to there is the glycol (b2) of specific quantity molecular-weight average and/or triol as polyhydroxy reactant (B) by using the polyester glycol (b1) with specific quantity molecular-weight average and using, and can realize and then performance above on an equal basis in the past, and working life can be improved simultaneously.
As polyester glycol (b1), include, for example: make the polycarboxylic acids such as terephthalic acid, m-phthalic acid, hexanodioic acid, nonane diacid, sebacic acid or these dialkyl or these mixture, with such as ethylene glycol, propylene glycol, Diethylene Glycol, butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, the glycolss such as 5-pentanediol, 3,3-dihydroxymethyl heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether diol or these mixture reaction and the polyester glycol obtained.Can enumerate in addition: by above-mentioned polycarboxylic acid or these dialkyl or these mixture, carry out ring-opening polymerization with the lactone such as polycaprolactone, poly-valerolactone, poly-(Beta-methyl-γ-valerolactone) and the polyester glycol etc. that obtains.
By the polyester glycol (b1) that usage quantity molecular-weight average is in above-mentioned scope, and become good with using polyether polyurethane as the intermiscibility of the above-mentioned polisocyanate component (A) of necessary constituent, and transparent adhesive composition can be obtained, and sufficient then performance can be shown.
Be more than 50 as number average molecular weight and be less than 500 glycol (b2), include, for example: polyester glycol, polyether glycol, polyether ester glycol, polyesteramide glycol, acrylic acid series glycol, polycarbonate diol; Ethylene glycol, propylene glycol, Diethylene Glycol, butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 3,3-dihydroxymethyl heptane, 2-methyl isophthalic acid, the low-molecular-weight diol classes such as ammediol; Or these mixture.In these, with regard to reactive viewpoint, be preferably low-molecular-weight diol class.
As above-mentioned polyester glycol, include, for example: make terephthalic acid, m-phthalic acid, hexanodioic acid, nonane diacid, the diprotic acid such as sebacic acid or these dialkyl or these mixture, with such as ethylene glycol, propylene glycol, Diethylene Glycol, butyleneglycol, neopentyl glycol, 1, 6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 3, 3 '-dihydroxymethyl heptane, polyoxyethylene glycol, polyoxypropylene glycol etc. 2 functional glycol class or these mixture reaction and the polyester glycol obtained, or by polycaprolactone, poly-valerolactone, the polyester glycol that lactone such as poly-(Beta-methyl-γ-valerolactones) is carried out ring-opening polymerization and obtained.
As above-mentioned polyether glycol, include, for example: will such as water, ethylene glycol, propylene glycol etc. 2 official can harmonic component polyvalent alcohol as initiator, the epoxy compoundss such as oxyethane, propylene oxide, butylene oxide ring, tetrahydrofuran (THF) are carried out being polymerized and the polyether glycol that obtains.
As above-mentioned polyester ether polylol, include, for example: make the diprotic acid such as terephthalic acid, m-phthalic acid, hexanodioic acid, nonane diacid, sebacic acid or these dialkyl or these mixture, react with above-mentioned polyether glycol and the polyether ester glycol obtained.
As above-mentioned polyesteramide glycol, when above-mentioned esterification, such as, obtain as raw material in the lump by quadrol, propylene diamine, hexamethylene-diamine etc. being had amino aliphatie diamine.
As the example that aforesaid propylene acid is glycol, by the methacrylic acid derivative etc. of the Hydroxyethyl Acrylate, hydroxypropyl acrylate, hydroxy butyl acrylate etc. or these correspondence that will comprise more than 1 hydroxyl in 1 molecule, carry out copolymerization with such as vinylformic acid, methacrylic acid or its ester and obtain.
As above-mentioned polycarbonate diol, include, for example: by making to be selected from ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,5-PD, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 1,9-nonanediol, 1,8-nonanediol, neopentyl glycol, Diethylene Glycol, dipropylene glycol, Isosorbide-5-Nitrae-cyclohexanediol, 1, one or more glycol in 4-cyclohexanedimethanol, to react with methylcarbonate, diphenyl carbonate, ethylene carbonate, phosgene (phosgene) etc. and to obtain.
Be more than 50 as number average molecular weight and be less than 500 triol (b3), can enumerate: polyether triol, Viscotrol C; The low molecule such as TriMethylolPropane(TMP), glycerine three alcohols; Or these mixture.In these, with regard to reactive viewpoint, be preferably low molecule three alcohols or polyether triol.
As above-mentioned polyether triol, include, for example: use the such as synthesis of epoxy compounds such as the harmonic component such as TriMethylolPropane(TMP), glycerine triol and oxyethane, propylene oxide, butylene oxide ring, tetrahydrofuran (THF) and the polyether triol obtained.
Polyhydroxy reactant (B) is in polyhydroxy reactant (B) 100 quality %, preferably comprise: more than glycol (b1) 60 quality %, below 99 quality %, more than total 1 quality %, below the 40 quality % of glycol (b2) and triol (b3).Be above-mentioned scope by the ratio of components of glycol (b1) etc., and sufficient working life and then performance can be shown.Preferred scope is, in polyhydroxy reactant (B) 100 quality %, be more preferably and comprise: more than glycol (b1) 80 quality %, below 95 quality %, more than total 5 quality %, below the 20 quality % of glycol (b2) and triol (b3).
Polyhydroxy reactant (B), except above-mentioned glycol (b1), glycol (b2), triol (b3), in the scope not damaging object of the present invention, can comprise other polyhydroxy reactants.
Adhesive composition of the present invention is when being set to 100 moles by the hydroxyl moles in polyhydroxy reactant (B), and the isocyanate group mole number in polisocyanate component (A) is preferably more than 70 moles, less than 300 moles.By isocyanate group mole number is set to more than 70 moles, and there is sufficient Bonding strength, and when isocyanate group mole number is below 300 moles, the state of the adhesion agent layer on evaporation face can be formed well.The preferred scope of higher limit is less than 250 moles, and especially preferred scope is less than 230 moles, and the preferred scope of lower value is more than 100 moles, and especially preferred scope is more than 150 moles.
Adhesive composition of the present invention is preferably not containing solvent.When lacking the mobility of each composition, allocate after being preferably the degree being heated to each composition respectively can guarantee mobility.If can mobility be guaranteed, then can not heat when allocating.
By above-mentioned polisocyanate component (A), polyhydroxy reactant (B) composition, other the firm mixed viscosity such as aftermentioned various additives, at at least arbitrary temperature of the temperature ranges of 25 DEG C ~ 50 DEG C, be preferably more than 50mPas, 5, below 000mPas, be more preferably more than 100mPas, 3, below 000mPas.
In addition, in the present invention, after so-called just mixing, refer to that after Homogeneous phase mixing within 5 minutes, viscosity utilizes the value calculated by Brookfield viscometer to represent.When viscosity is all more than 5,000mPas at arbitrary temperature of the temperature range of 25 DEG C ~ 50 DEG C, has and be difficult to coating and be difficult to guarantee good workability, even if application temperature to be increased to the possibility that 100 DEG C also cannot obtain good application outward appearance.In addition, if apply more than 100 DEG C, then there is film to extend and cause the spacing skew of printing decorative pattern, and tendency that cannot be laminated.On the other hand, when at arbitrary temperature of the temperature range of 25 DEG C ~ 50 DEG C, viscosity is all less than 50mPas, when having original cohesion weak and cannot obtain sufficient then performance or apply solid on base material, the thickness of film becomes uneven and produces the tendency of bad order or generation warpage.
Adhesive composition of the present invention can use the additives such as such as antioxidant, UV light absorber, anti hydrolysis agent, anti-emblem drug, tackifier, fluidizer, defoamer, pigment, weighting agent as required further.In addition, in order to improve then performance further, and the then auxiliary agent such as silane coupling agent, phosphoric acid, phosphoric acid derivatives, acid anhydrides, tackiness resin can be used.In addition, in order to regulate sclerous reaction, and known catalyzer, additive etc. can be used.
The using method of adhesive composition of the present invention is not particularly limited, and as preferred method, can illustrate following method.That is, by polisocyanate component (A), polyhydroxy reactant (B) mixing, solventless laminating machine (laminater) is utilized adhesive composition to be coated the surface of flat substrates.The glue spread of adhesive composition is suitably selected according to the kind of base material or coating condition etc., is generally 1.0g/m 2above, 5.0g/m 2below, 1.5g/m is preferably 2above, 4.5g/m 2below.
Then, the commissure of flat substrates and other flat substrates are fitted, at normal temperature or heat lower aging and make it harden.When for adhesive composition of the present invention, the aging required time is about 1 day.In addition, when for adhesive composition of the present invention, even if ambient moisture height when being certainly applied to aging also can show fully then performance.
The adhesive composition laying sheets base material of the application of the invention and can duplexer be obtained.As flat substrates, can use: the plastic film of polyester, polymeric amide, polyethylene, polypropylene etc., evaporation has the metal deposition film of aluminium, silicon oxide, aluminum oxide etc., the tinsel etc. of stainless steel, iron, copper, lead etc.The combination of this base material can be plastic film each other, also can be plastic film and metal deposition film or tinsel.
In above-mentioned patent documentation 5, as described above, there is the short problem working life of adhesive composition.In patent documentation 5, disclose polyhydroxy reactant (b) and preferably only comprise triol (the 52nd section, the 54th section etc.), but triol is rich reactive compared with diol component, therefore infer after polyhydroxy reactant mixes with polisocyanate component, meeting is extreme increased viscosity at short notice, and causes shorten the working life of adhesive composition.
On the other hand, according to the present invention, due to use specific quantity molecular-weight average polyester glycol (b1), with the glycol (b2) of specific quantity molecular-weight average and/or triol (b3) as polyhydroxy reactant, and above-mentioned polyhydroxy reactant (B) is used in above-mentioned polisocyanate component (A), ambient moisture is not strictly managed into low humidity even if therefore can provide, also can be aging and show equal above then performance with the time short than before, and the adhesive composition that working life is long.Particularly when no-solvent type solid, viscosity increase in short period of time can cause tremendous influence to screening characteristics, productivity, therefore with regard to the viewpoint of industry, large problem is become, but according to adhesive composition of the present invention, as described above when no-solvent type, even if ambient moisture is not strictly managed into low humidity, also can be aging and show equal above then performance with the time short than before, and long working life can be realized.
" embodiment "
Below, by embodiment, the present invention is further illustrated.% in embodiment and comparative example and part as long as no special instructions, are quality criteria entirely.
The number average molecular weight of polyether glycol, polyester glycol etc. utilizes gel permeation chromatography (Gel Permeation Chromatography, GPC) to obtain.It is measure under the following conditions surely that quantity mean molecule is measured.Machine: eastern Cao (TOSOH) HLC-8220GPC, tubing string: TSKGEL SuperHM-M, solvent: tetrahydrofuran (THF) (Tetrahydrofuran, THF), solution take-off rate: 0.6ml per minute, temperature: 40 DEG C, detector: Differential refractometer, molecular weight standard: polystyrene
Acid number, hydroxyl value represent with the mg of the KOH of the polymer polyatomic alcohol of every 1g.Acid number measures by utilizing the neutralization titration of KOH, and hydroxyl value measures by using the acetylize of pyridine and diacetyl oxide.In addition, NCO containing ratio represents with mass fraction the isocyanic ester base unit weight be present in sample.NCO containing ratio is that the toluene solution adding excessive dibutylamine makes it react, and after generating suitable urea, uses hydrochloric acid standard solution, carries out back titration, thus measure by indicator titration method.
(synthesis example 1) drops into and makes water and propylene oxide addition and 2 officials that the number average molecular weight that obtains is about 400 can polypropylene glycols 30 parts, number average molecular weight be about 2 in reaction vessel, 2 officials of 000 can polypropylene glycols 40 parts, make glycerine and propylene oxide addition and the number average molecular weight that obtains be about 400 3 officials' energy polypropylene glycols 20 parts, 4,4 '-diphenylmethanediisocyanate 40 parts and 2,4 '-diphenylmethanediisocyanate 60 parts, stirs under nitrogen flowing with 70 DEG C ~ 80 DEG C heating 3 hours and carries out urethane reaction.Obtain the polyether polyurethane polyisocyanate resin with isocyanate group.Isocyanate group containing ratio is 14.4%.Below, this resin is designated as polymeric polyisocyanate A-(1).
(synthesis example 2) setting 4,4 '-diphenylmethanediisocyanate: 70 parts, 2,4 '-diphenylmethanediisocyanate: 10 parts, in addition, in the mode identical with synthesis example 1, obtain the polyether polyurethane polyisocyanate resin with isocyanate group.Isocyanate group containing ratio is 11.5%.Below, this resin is designated as polymeric polyisocyanate A-(2).
(synthesis example 3) setting 4,4 '-diphenylmethanediisocyanate: 76 parts, 2,4 '-diphenylmethanediisocyanate: 38 parts, in addition, in the mode identical with synthesis example 1, obtain the polyether polyurethane polyisocyanate resin with isocyanate group.Isocyanate group containing ratio is 16.5%.Below, this resin is designated as polymeric polyisocyanate A-(3).
(synthesis example 4) setting 4,4 '-diphenylmethanediisocyanate: 100 parts, and do not use 2,4 '-diphenylmethanediisocyanate, in addition, in the mode identical with synthesis example 1, obtain the polyether polyurethane polyisocyanate resin with isocyanate group.Isocyanate group containing ratio is 14.4%.Below, this resin is designated as polymeric polyisocyanate A-(4).
(synthesis example 5) does not use 4,4 '-diphenylmethanediisocyanate, and setting 2,4 '-diphenylmethanediisocyanate: 100 parts, in addition, in the mode identical with synthesis example 1, obtain the polyether polyurethane polyisocyanate resin with isocyanate group.The amount of isocyanate group is 14.4%.Below, this resin is designated as polymeric polyisocyanate A-(5).
(synthesis example 6) does not use 4,4 '-diphenylmethanediisocyanate and 2,4 '-diphenylmethanediisocyanate, replace setting isophorone diisocyanate (IPDI): 90 parts, in addition, in the mode identical with synthesis example A-1, obtain the polyether polyurethane polyisocyanate resin with isocyanate group.The amount of isocyanate group is 14.6%.Below, this resin is designated as polymeric polyisocyanate A-(6).
[table 1]
(synthesis example 7) drops into m-phthalic acid 438 parts, ethylene glycol 106 parts, neopentyl glycol 179 parts in reaction vessel, stirs under nitrogen flowing and is heated to 150 DEG C ~ 240 DEG C and carries out esterification.When acid number becomes 1.3 (mgKOH/g), temperature of reaction is set to 200 DEG C, and reaction vessel interior is reduced pressure lentamente, below 1.3kPa reaction 30 minutes, and obtain the polyester glycol resin at two ends with hydroxyl that acid number is 0.4 (mgKOH/g), hydroxyl value is 137 (mgKOH/g), number average molecular weight is about 800.Below, this polyvalent alcohol is designated as polyvalent alcohol (b1)-1.
(synthesis example 8) drops into m-phthalic acid 373 parts, terephthalic acid 42 parts, ethylene glycol 109 parts, neopentyl glycol 182 parts in reaction vessel, stirs under nitrogen flowing and is heated to 150 DEG C ~ 240 DEG C and carries out esterification.When acid number becomes 1.3 (mgKOH/g), temperature of reaction is set to 200 DEG C, and reaction vessel interior is reduced pressure lentamente, below 1.3kPa reaction 30 minutes, and obtain the polyester glycol resin at two ends with hydroxyl that acid number is 0.5 (mgKOH/g), hydroxyl value is 184 (mgKOH/g), number average molecular weight is about 600.Below, this resin is designated as polyester glycol (b1)-2.
(synthesis example 9) drops into m-phthalic acid 298 parts, hexanodioic acid 262 parts, ethylene glycol 341 parts, Diethylene Glycol 219 parts in reaction vessel, stirs under nitrogen flowing and is heated to 150 DEG C ~ 240 DEG C and carries out esterification.When acid number becomes 1.3 (mgKOH/g), temperature of reaction is set to 200 DEG C, and reaction vessel interior is reduced pressure lentamente, below 1.3kPa reaction 30 minutes, and obtain the polyester glycol resin at two ends with hydroxyl that acid number is 0.5 (mgKOH/g), hydroxyl value is 40.7 (mgKOH/g), number average molecular weight is about 2,800.Below, this resin is designated as polyester glycol (b1)-3.
(synthesis example 10) drops into m-phthalic acid 186 parts, hexanodioic acid 383 parts, neopentyl glycol 429 parts in reaction vessel, stirs under nitrogen flowing and is heated to 150 DEG C ~ 240 DEG C and carries out esterification.When acid number becomes 1.3 (mgKOH/g), temperature of reaction is set to 200 DEG C, and reaction vessel interior is reduced pressure lentamente, below 1.3kPa reaction 30 minutes, and obtain the polyester glycol resin at two ends with hydroxyl that acid number is 0.4 (mgKOH/g), hydroxyl value is 27.3 (mgKOH/g), number average molecular weight is about 4,000.Below, this resin is designated as polyester glycol (b1)-4.
(synthesis example 11) drops into cis-Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid 310 parts, 1,4 cyclohexane dimethanol 415 parts in reaction vessel, stirs under nitrogen flowing and is heated to 150 DEG C ~ 220 DEG C and carries out esterification.When acid number becomes 3.0 (mgKOH/g), temperature of reaction is set to 200 DEG C, and reaction vessel interior is reduced pressure lentamente, below 1.3kPa reaction 30 minutes, and obtain the polyester glycol resin at two ends with hydroxyl that acid number is 2.0 (mgKOH/g), hydroxyl value is 332 (mgKOH/g), number average molecular weight is about 300.Below, this resin is designated as polyester polyol (b2)-1.
(embodiment 1) drops into the polymeric polyisocyanate A-(1) of gained in 200 parts of synthesis examples 1 in a reservoir, under nitrogen flowing while stir, while add polyester glycol (b1)-1, the Diethylene Glycol 10 parts of gained in 90 parts of synthesis examples 7, mix in the warm water bath of 25 DEG C, and obtain no-solvent type adhesive composition.
Within 5 minutes, measure the viscosity 25 DEG C time of said composition after Homogeneous phase mixing, result is 2,500mPas.
In addition, in above-mentioned no-solvent type adhesive composition, the hydroxyl relative in polyhydroxy reactant: 100 moles, and containing being derived from the isocyanate group 166 moles of polymeric polyisocyanate A-(1).Relative to the amount of the isocyanate group of 100 hydroxy, obtain as follows.
Relative to amount=[isocyanate group (eq.)/hydroxyl (eq.)] × 100 of the isocyanate group of 100 hydroxy
Isocyanate group (eq.)=NCO containing ratio (quality %)/(42 × 100)
Hydroxyl (eq.)=56110/ hydroxyl value
NCO containing ratio (quality %) obtains according to JIS K7301, and hydroxyl value obtains according to JIS K1557-1.
Evaluate the working life of the no-solvent type adhesive composition of gained by the following method.In addition, use the no-solvent type adhesive composition of gained, obtain duplexer according to following method, and evaluate the adhesion of duplexer, the interfacial state of duplexer.The results are shown in table 2.
(embodiment 2 ~ embodiment 11, comparative example 1 ~ comparative example 8) uses table 2 and the polisocyanate component (A) shown in table 3 and polyhydroxy reactant (B) with specified proportion, in addition, operate in the same manner as example 1, and obtain no-solvent type adhesive composition.In addition, in the same manner as example 1, working life, the adhesion of duplexer and the interfacial state of duplexer is evaluated.The results are shown in table 2 and table 3.
In addition, usage quantity molecular-weight average is about 2, the embodiment 4 of the polyester glycol (b1)-3 of 800, embodiment 9, usage quantity molecular-weight average are about 4, in the comparative example 8 of the polyester glycol (b1)-4 of 000, after above-mentioned polyester glycol (b1)-3, polyester glycol (b1)-3 are heated to 70 DEG C respectively, mix with polymeric polyisocyanate A-(1) etc. in the warm water bath of 25 DEG C, and utilize Brookfield viscometer to measure the viscosity of mixing within latter 5 minutes.The temperature of adhesive composition during mensuration is about 50 DEG C.
The useless formulation adhesive composition of gained in each embodiment or comparative example is enclosed the vial with lid of the 250mL capacity of 200g by < > working life, utilize Brookfield viscometer be determined in 50 DEG C of warm water baths through time 30 minutes after viscosity, study working life thus.The temperature of adhesive composition during mensuration is about 50 DEG C.
[making of duplexer] utilizes solvent-free test coated machine the no-solvent type adhesive composition being adjusted to gained in each embodiment of 50 DEG C or comparative example to be coated the surface (glue spread: 2.0g/m of polyethylene terephthalate (Polyethylene Terephthalate, PET) film (thickness: 12 μm) at 70 DEG C 2), the evaporation face without extended polypropylene film (VMCPP, thickness: 25 μm) of overlapping AM aluminum metallization on its coated face, and obtain the duplexer (pre-duplexer) of preparatory stage.By these pre-duplexers 25 DEG C, carry out under the environment of humidity 60%RT or 80%RT 1 day or 2 days aging and storage periods, and make duplexer.Observe, measure the interfacial state of adhesion and duplexer according to each duplexer of following main points to gained, these result is shown in table 2 and table 3.
Duplexer is cut into that length is 300mm, width is 15mm by (adhesion), and as test piece.Use Instron (Instron) type tensile testing machine, be that the peeling rate of 300mm/ minute stretches with peeling rate under the environment of 25 DEG C, and measure the T-shaped stripping strength (N/15mm) between PET/VMCPP.This test is carried out 5 times, and obtains its mean value.
(interfacial state of duplexer) to duplexer from PET film side the evaporation face through PET film visual observation substrate, by the interfacial state (state of the adhesion agent layer on evaporation face) of following benchmark evaluation duplexer.
Zero: without orange peel shape pattern or little mottled pattern on evaporation face, adhesion agent layer is even.
△: observe a little orange peel shape pattern or little mottled pattern on evaporation face, but for using the level of upper no problem.
×: on evaporation face, observe a large amount of orange peel shape patterns or little mottled pattern.
Known according to table 2, in embodiment 1 ~ embodiment 11, the adhesion agent layer on evaporation face in good condition, and Bonding strength is also excellent.Particularly in embodiment 1, embodiment 2, even if aging time ambient moisture high, also can show sufficient Bonding strength at short notice.In contrast, only use be derived from 4, the composition of 4 '-MDI is as in the comparative example 1 of isocyanate prepolymer composition, the impact of ambient moisture when being obviously subject to aging, 25 DEG C, aging under 80%RT environment time, the state of the adhesion agent layer on evaporation face is obviously poor, and Bonding strength is also minimum.In addition, be derived from 2 only using, the composition of 4 '-MDI as isocyanate prepolymer composition comparative example 2, only use in the comparative example 3 of isophorone diisocyanate known, although adhesion agent layer on evaporation face is in good condition, Bonding strength is obviously poor.In addition, when for comparative example 3, temperature when initial viscosity measures is 25 DEG C, and the temperature of the viscosimetric analysis after mixing after 30 minutes is 50 DEG C, therefore can find that the viscosity after 30 minutes reduces at a glance.When for the embodiment of use 2,4 '-MDI and 4,4 '-MDI or comparative example, even if temperature when measuring is different, the reason that the viscosity after 30 minutes is also large is, carries out the reaction with polyhydroxy reactant (A).In other words, isophorone diisocyanate and 2,4 '-MDI and 4,4 '-MDI compares reactive poor, at 50 DEG C about 30 minutes time, not too can carry out the reaction with polyhydroxy reactant (A), therefore almost not observe viscosity and rise, and observe the apparent viscosity (apparent viscosity) caused because measuring the impact of temperature and reduce.In addition, the obviously little reason of Bonding strength is inferred when being (25 DEG C × 1 day or 2 days) aging between low-temperature short-time, not too can react.
In addition, not containing in low-molecular-weight glycol (b2) or the comparative example 4 of triol (b3) as polyhydroxy reactant (B), although adhesion agent layer on known evaporation face is in good condition, Bonding strength is obviously poor.And, only using low molecular weight diols (b2) or triol (b3) as polyhydroxy reactant (B) (comparative example 5, comparative example 6, comparative example 7) or using Mn to be 4, when the polyester glycol (b1)-4 of 000 is as polyester glycol (b1) (comparative example 8), the state of the adhesion agent layer on known evaporation face is also poor, and Bonding strength is obviously poor.
In addition, in comparative example 7, although firm mixed viscosity is no less than embodiment, but because polyhydroxy reactant (B) only comprises low-molecular-weight triol (b3), therefore many with the reflecting point of polisocyanate component (A), and form the result that viscosity at short notice obviously rises.
The application advocates based on the Japanese publication Patent 2013-9142 filed an application on January 22nd, 2013 and the right of priority of Japanese publication Patent 2013-247979 of filing an application on November 29th, 2013, and its all disclosure is incorporated in the application.
[utilizability in industry]
Adhesive composition of the present invention is suitable as the purposes various plastic film being fitted each other and plastic film and metal deposition film or tinsel are fitted, and the wrapping material being particularly suitable as food, medical product, makeup etc. are formed with laminated solid.In addition, although be suitable for the film joint each other of film like, thickness indefinite, also can preferably use adhesive composition of the present invention in the joint of different shape or form.And adhesive composition of the present invention, owing to being preferably used for no-solvent type, therefore can be widely used in all solvent-free solids.

Claims (8)

1. an adhesive composition, it comprises: polisocyanate component (A); And polyhydroxy reactant (B),
Described polisocyanate component (A) makes to have 2,4 '-diphenylmethanediisocyanate (a1) and 4, the isocyanic ester of 4 '-diphenylmethanediisocyanate (a2),
With the polyvalent alcohol must with polyether glycol (a3), the reactive products of reacting under the condition that isocyanate group is excessive,
Described polyhydroxy reactant (B) is polyhydric alcohol composition, must have number average molecular weight is more than 500,3, the polyester glycol (b1) of less than 000, and comprise number average molecular weight be more than 50 and be less than 500 glycol (b2) and number average molecular weight be more than 50 and be less than the triol (b3) of 500 at least any one.
2. adhesive composition according to claim 1, wherein at 2,4 '-diphenylmethanediisocyanate (a1) and 4, in the total 100 % by mole of 4 '-diphenylmethanediisocyanate (a2),
2,4 '-diphenylmethanediisocyanate (a1) is more than 10 % by mole, less than 60 % by mole,
4,4 '-diphenylmethanediisocyanate (a2) is more than 40 % by mole, less than 90 % by mole.
3. adhesive composition according to claim 1 and 2, wherein comprises in polyhydroxy reactant (B) 100 quality %:
More than polyester glycol (b1) 60 quality %, below 99 quality %;
More than total 1 quality %, below the 40 quality % of glycol (b2) and triol (b3).
4. adhesive composition according to any one of claim 1 to 3, it is characterized in that: when the hydroxyl moles in polyhydroxy reactant (B) is set to 100 moles, the mole number of the isocyanate group in polisocyanate component (A) is more than 70 moles, less than 300 moles.
5. adhesive composition according to any one of claim 1 to 4, it is no-solvent type.
6. adhesive composition according to any one of claim 1 to 5, is characterized in that: it is the laminated solid of wrapping material formation.
7. a duplexer, it uses adhesive composition according to any one of claim 1 to 6 to carry out stacked at least two flat substrates to form.
8. the manufacture method of a duplexer, adhesive composition according to any one of claim 1 to 6 is coated on the 1st flat substrates and forms adhesion agent layer by it, and in described adhesion agent layer overlapping 2nd flat substrates, by the described adhesion agent layer sclerosis between two flat substrates.
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