CN102264857A - Heat-resistant moisture-curable adhesive composition for polycarbonate resin - Google Patents

Heat-resistant moisture-curable adhesive composition for polycarbonate resin Download PDF

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Publication number
CN102264857A
CN102264857A CN2009801525076A CN200980152507A CN102264857A CN 102264857 A CN102264857 A CN 102264857A CN 2009801525076 A CN2009801525076 A CN 2009801525076A CN 200980152507 A CN200980152507 A CN 200980152507A CN 102264857 A CN102264857 A CN 102264857A
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China
Prior art keywords
polycarbonate resin
mentioned
polycarbonate
adhesive composite
polytetramethylene glycol
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CN2009801525076A
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Chinese (zh)
Inventor
马渊俊介
堀大祐
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Cemedine Co Ltd
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Cemedine 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
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2081—Heterocyclic amines; Salts thereof containing at least two non-condensed heterocyclic rings
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • 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
    • 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
    • C08G18/44—Polycarbonates
    • 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
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • 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
    • C09J169/00—Adhesives based on polycarbonates; Adhesives based on derivatives of polycarbonates
    • 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

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Provided is a heat-resistant moisture-curable adhesive composition for a polycarbonate resin having excellent heat resistance, adhesiveness to polycarbonate, and workability. The adhesive composition for a polycarbonate resin to be used for bonding polycarbonate resins to each other, comprises (A) a urethane prepolymer having an isocyanate group at a terminal thereof obtained by reacting a polyisocyanate with at least one polyol selected from a group consisting of polytetramethylene glycols, modified polytetramethylene glycols, and polycarbonate polyols, and (B) at least one curing catalyst selected from a group consisting of tertiary amine catalysts and tin catalysts.

Description

Thermotolerance one liquid moisture-curable polycarbonate resin adhesive composite
Technical field
The present invention relates to engage polycarbonate resin polycarbonate resin adhesive composite each other, relate in particular to a kind of thermotolerance and the liquid moisture-curable polycarbonate resin adhesive composite excellent in adhesion of polycarbonate.
Background technology
Electronic component material uses engineering plastics, PC (polycarbonate) PS (polystyrene) PPS (polyphenylene sulfide) PPOPETPBT (polybutylene terepthatlate) etc., and from the thermotolerance viewpoint, polycarbonate especially is widely used.
Polycarbonate caking agent aspect, patent documentation 1 have disclosed by end to be had the 1st composition (A) that the mixture of polyfunctional isocyanate's compound of isocyanate group and organo-tin compound constitutes, has the 2nd composition (B) that the mixture of the polycarbonate diol of OH base constitutes with multifunctional sulfhydryl compound that is had sulfydryl by end and two ends and cooperate the binary type polycarbonate caking agent that forms.Patent documentation 1 described caking agent has the initial stage cementability to polycarbonate, but owing to be 2 liquid types, so in operation, mixing etc. needs the time.
Polycarbonate caking agent as 1 liquid type, patent documentation 2 disclosed engage polycarbonate resin plate each other 1, the 4-diox, with 1,1, the 1-trichloroethane, be selected from the polycarbonate resin plate solvent type adhesive that at least a kind of solvent in acetate, methyl iso-butyl ketone (MIBK) and the normal-butyl alcohol forms.Patent documentation 2 described caking agents have excellent cementability to polycarbonate, but because of containing solvent problem are being arranged on the environment and on the job safety.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese kokai publication hei 2-155979 communique
[patent documentation 2] Japanese kokai publication hei 4-77590 communique
Summary of the invention
[problem that invention institute desire solves]
The objective of the invention is to, provide thermotolerance, the cementability of polycarbonate and a liquid moisture-curable polycarbonate resin adhesive composite of operability excellence.
[solving the means of problem]
For solving above-mentioned problem, thermotolerance one liquid moisture-curable polycarbonate resin adhesive composite of the present invention is to engage polycarbonate resin polycarbonate resin adhesive composite each other, it is characterized in that, the end that contains the polyvalent alcohol more than a kind that is selected from polytetramethylene glycol, modification polytetramethylene glycol and the polycarbonate polyol and polyisocyanates reaction gained have the carbamate prepolymer (A) of isocyanate group and be selected from tertiary amine catalyst and tin catalyst in the curing catalysts more than a kind (B).
Thermotolerance one liquid moisture-curable polycarbonate resin of the present invention preferably also contains silicon-dioxide (C) with adhesive composite.
Above-mentioned relatively carbamate prepolymer (A) 100 mass parts preferably cooperate above-mentioned curing catalysts (B) 0.01～10 mass parts.
[effect of invention]
Adhesive composite thermotolerance of the present invention and excellent to the cementability of polycarbonate, as require thermotolerance and the caking agent that the electrical apparatus product of the cementability of polycarbonate or the assembling of precision machinery are used etc., affixed dose, have excellent properties, and low viscosity and the excellent unusual effect of prolonged preservation stability are arranged.In addition, adhesive composite of the present invention is a liquid system, utilizes airborne moisture and curing at normal temperatures, so operability is excellent.
Embodiment
Embodiments of the present invention below are described, but these are illustration only, and all changes that do not break away from technological thought scope of the present invention are also included within the scope of the present invention.
Adhesive composite of the present invention is for engaging polycarbonate resin polycarbonate resin each other adhesive composite, contain polyvalent alcohol and polyisocyanates the reaction gained end have the carbamate prepolymer (A) of isocyanate group and be selected from tertiary amine catalyst and tin catalyst in the curing catalysts more than a kind (B), and as above-mentioned polyvalent alcohol, comprise be selected from polytetramethylene glycol, modification polytetramethylene glycol and the polycarbonate polyol more than a kind.
As above-mentioned polytetramethylene glycol, can use known tetrahydrofuran polymer.Though the molecular weight of above-mentioned polytetramethylene glycol is restriction especially, preferably use number-average molecular weight 500～5000, more preferably use the polytetramethylene glycol of 500～2000 scope.Above-mentioned polytetramethylene glycol can use separately or be used in combination more than 2 kinds.
Above-mentioned modification polytetramethylene glycol is the multipolymer of tetramethylene ether and alkylene ether (alkylene ether), and above-mentioned alkylene ether preferably has side chain.As above-mentioned modification polytetramethylene glycol, can enumerate multipolymer, the tetrahydrofuran (THF) of for example multipolymer, tetrahydrofuran (THF) and the alkylene oxide of tetrahydrofuran (THF) and alkyl substituted tetrahydro furans and have the multipolymer etc. of the alkylene ether of side chain.The multipolymer of above-mentioned tetrahydrofuran (THF) and alkyl substituted tetrahydro furans as preference, can be enumerated multipolymer of for example described tetrahydrofuran (THF) of Japanese kokai publication sho 63-235320 communique and 3-alkyl tetrahydro furans etc.
Though the molecular weight of above-mentioned modification polytetramethylene glycol is restriction especially, but preferred use number-average molecular weight 500～5000, more preferably use the material of 1000～3000 scope.Above-mentioned modification polytetramethylene glycol can use separately or be used in combination more than 2 kinds.
Above-mentioned polycarbonate polyol, the polyvalent alcohol of the structure shown in the preferred following general formula of tool (1).
[changing 1]
Figure BDA0000070988040000031
In the above-mentioned formula (1), X is the hydrocarbon system base, and n is a natural number, R 1Be chain alkylidene groups, 1 such as straight-chain alkyl-sub-, isopropylidene, sec.-butylidene, uncle's butylidene such as methylene radical, ethylidene, positive propylidene, 1-cyclohexylene, 1,2-cyclohexylene, 1,3-cyclohexylene or 1, bisphenol type skeletons such as ether, dihydroxyphenyl propane, Bisphenol F, bisphenol S such as the arylidene of ester ring type hydrocarbon system base, phenylene, naphthylidenes etc. such as 4-cyclohexylene, inferior methoxyl group, inferior propoxy-etc., also expression repeats once above structure respectively sometimes.In addition, R 1Also can be by groups that various substituting group replaced such as halogen radicals such as fluorine, chlorine, bromine, cyano group, carboxyl, sulfonic group, nitro, hydroxyl, alkoxyl groups.In addition, R 1Can also be endways, contain unsaturated groups such as one or more vinylidenes or carbonyl, carboxyl, ether, thioether group, carbamate groups, urea groups, thioureido etc. in two ends, inside or the repeating unit.In addition, R 1Can distinguish identical or different.
Though the molecular weight of above-mentioned polycarbonate polyol is restriction especially, preferably use number-average molecular weight 300～3000, more preferably use the material of 500～2000 scope.Above-mentioned polycarbonate polyol can use separately or be used in combination more than 2 kinds.
Above-mentioned polytetramethylene glycol, modification polytetramethylene glycol and polycarbonate polyol can only use more than a kind or 2 kinds and be used in combination, and there is no particular restriction in combination, set out by the operability viewpoint, preferably uses the modification polytetramethylene glycol.Make up when polyvalent alcohol uses more than 2 kinds, but polyvalent alcohol more than 2 kinds and polyisocyanates reaction synthesis of carbamates prepolymer (A), or the different carbamate prepolymer more than 2 kinds (A) of polyol blend composition uses.
In the present invention, as polyhydroxy reactant, can cooperate above-mentioned polytetramethylene glycol, modification polytetramethylene glycol and polycarbonate polyol other polyvalent alcohol in addition.When cooperating other polyvalent alcohol, the total amount of above-mentioned polytetramethylene glycol, modification polytetramethylene glycol and polycarbonate polyol is preferably more than the 10 quality % in general with respect to polyvalent alcohol, more preferably more than the 30 quality %.
As long as above-mentioned other polyvalent alcohol is for having the active hydrogen base active hydrogen-contg compound more than 2, not restriction especially, can enumerating polyvalent alcohol that 3 officials for example can be above or glycol, polypropylene glycol (PPG), to wait other polyether glycol, polyester polyol, polybutadiene polyol, polyisoprene polyvalent alcohol, polyolefin polyhydric alcohol, polymer polyatomic alcohol, polycaprolactone polyol, polyacrylic ester be polyvalent alcohol etc., and these polyvalent alcohols can use separately or more than 2 kinds and use.
As above-mentioned polyisocyanates, be not particularly limited, can use known polyisocyanate compound with 2 above isocyanate group, can enumerate for example diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), Xylene Diisocyanate (XDI), aromatic polyisocyanate classes such as naphthalene diisocyanate, in addition, hexamethylene diisocyanate (HDI) is still arranged, aliphatic polyisocyante classes such as Methionin methyl ester vulcabond, hydrogenated diphenyl methane diisocyanate, isophorone diisocyanate, norbornene alkyl diisocyanate, ester ring type polyisocyanates such as hydrogenated tolylene diisocyanate.As above-mentioned polyisocyanates, set out by cost and reactive view, preferred MDI, but if XDI is then preferably used in variable colors such as consideration xanthochromia.
The method of above-mentioned polyhydroxy reactant and above-mentioned polyisocyanates reaction is not limited especially, can use known method.On concrete, make that polyhydroxy reactant with 2 above hydroxyls (OH) is excessive in isocyanate group with the polyisocyanates with 2 above isocyanate group (NCO), just the NCO/OH equivalence ratio is reacted greater than 1 time, can obtain the carbamate prepolymer that end has isocyanate group.
This reaction conditions is restriction especially, for example in the ratio of NCO/OH equivalence ratio 1.3～10.0, more preferably under 1.5～5.0 the ratio, in nitrogen or the dry air air-flow, carry out a few hours reaction and make with 70～100 ℃.The NCO/OH equivalence ratio does not reach at 1.3 o'clock, and the viscosity of prepolymer uprises and operability has problem, surpasses 10 and produces bad situation because of foaming has.
In the adhesive composite of the present invention, can contain above-mentioned carbamate prepolymer (A) other known carbamate prepolymer in addition again.When cooperating other carbamate prepolymer, the total amount of above-mentioned carbamate prepolymer (A) is preferably more than the 10 quality % in general with respect to carbamate prepolymer in the adhesive composite of the present invention, more preferably more than the 30 quality %.
As above-mentioned other carbamate prepolymer, particularly, can enumerate the carbamate prepolymer that the end as other polyvalent alcohol except polytetramethylene glycol, modification polytetramethylene glycol and polycarbonate polyol and isocyanate compound reaction gained has isocyanate group.As long as above-mentioned other polyvalent alcohol is for having the active hydrogen-contg compound of 2 above active hydrogen bases, not restriction especially, for example can enumerating polyvalent alcohol that 3 officials can be above or glycol, polypropylene glycol (PPG), to wait other polyether glycol, polyester polyol, polybutadiene polyol, polyisoprene polyvalent alcohol, polyolefin polyhydric alcohol, polymer polyatomic alcohol, polycaprolactone polyol, polyacrylic ester be polyvalent alcohol etc., and these polyvalent alcohols can use separately or more than 2 kinds and use.
As employed tertiary amine catalyst in the above-mentioned curing catalysts (B), can be extensive use of known tertiary amine, for example monoamines such as triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutyl amine, tri-tert amine, three amylamines, three hexyl amines, trioctylphosphine amine, trisamine, methyl two 2-DEHAs, dibutyl 2-DEHA, three (hexadecyl) amine, tribenzyl amine; Tetramethyl-1, tetramethyl-1, polyamines such as 3-diaminopropanes, tetramethyl-hexamethylene-diamine, five methyl diethylentriamine; Triethylenediamine; N-ethylmorpholine, two (morpholino ethyl) ether, two (2, the 6-thebaine is for ethyl) ether, two (3, the 5-thebaine is for ethyl) ether, two (3, the 6-thebaine is for ethyl) ether, 4-(3,5-thebaine generation)-4 ' morpholinium compound such as Anaesthetie Ether etc.-(3,6-thebaine generation).
As the employed tin catalyst of above-mentioned curing catalysts (B), can be extensive use of known organo-tin compound, for example divalent organo-tin compound such as stannous octoate, naphthoic acid tin; The 4 valency organo-tin compounds such as reactant of dibutyl tin dicaprylate, dibutyltin dilaurate, dibutyl tin diacetate esters, dibutyl tin dimaleate, dibutyl tin two hard ester acid esters, dioctyl tin dilaurate, dioctyl tin two tertiary carbon acid esters, dibutyl tin oxide, dibutyl tin two (triethoxy silicon ester), dibutyl tin oxide and phthalic ester; The two tin such as (methyl ethyl diketones) of dibutyl tin are chelate compound etc.
Above-mentioned curing catalysts (B) though the cooperation ratio especially the restriction, preferably above-mentioned relatively carbamate prepolymer (A) 100 mass parts cooperate with 0.01～10 mass parts, more preferably cooperate with 0.01～2 mass parts.Above-mentioned tertiary amine catalyst and tin catalyst can use separately or also use more than 2 kinds.
Adhesive composite of the present invention preferably also contains silicon-dioxide (C).Above-mentioned silicon-dioxide (C) for example can be enumerated pyrogenic silica (fumed silica), burns till silicon-dioxide, sedimentation silicon-dioxide, pulverize silicon-dioxide, fused silica etc., preferably uses micropowder silicon-dioxide.
Above-mentioned silicon-dioxide (C) though the restriction especially of cooperation ratio, above-mentioned relatively carbamate prepolymer (A) 100 mass parts cooperate preferably with 0.5～30.0 mass parts, more preferably cooperate 3.0～15.0 mass parts.
Adhesive composite of the present invention is except that mentioned component, according to need, can cooperate filling agent, softening agent, tinting material, variable color to prevent that agent, bonding imparting agent, rerum natura from adjusting the various additives of thinners such as agent, releasing agent, lubricant, dewatering agent (storage stability modifying agent), tackifier, Antidrip agent, UV light absorber, antioxidant, hydrolysis stabilizer, fire retardant, radical polymerization initiator, high boiling solvent etc.
Above-mentioned filling agent is the organic or inorganic thing of different shape, for example can enumerate lime carbonate, magnesiumcarbonate, zinc carbonate; Carbon black; Clay; Talcum; Kaolin; Diatomite; Zeolite; Titanium oxide, unslaked lime, ferric oxide, zinc oxide, barium oxide, magnesium oxide; Tai-Ace S 150; Ethylene chloride is stuck with paste resin; Inanimate matter ball, organic balls etc. such as glass sphere, white sand ball, Saran ball, phenol ball, permalon ball; Or these lipid acid, fatty acid ester handled thing etc., can be used alone or as a mixture.In addition, can use inorganic hollow filler, and the organic hollow filler of polyvinylidene difluoride (PVDF) or polyvinylidene fluoride alkene copolymer etc. of glass sphere or silica spheres etc.
As above-mentioned softening agent, can enumerate for example dioctyl phthalic ester (DOP), dibutyl phthalate (DBP), dilauryl phthalic ester (DLP), butyl benzyl phthalic ester (BBP), the dioctyl adipic acid ester, the diisononyl phthalic ester, the diiso decyl adipic acid ester, the diiso decyl phthalic ester, the trioctylphosphine phosphoric acid ester, three (chloroethyl) phosphoric acid ester, three (two chloropropyls) phosphoric acid ester, hexanodioic acid propylene glycol polyester, hexanodioic acid butyleneglycol polyester, the hard ester acid alkyl ester of epoxy, epoxidised soybean oil etc. can be used alone or as a mixture.
Above-mentioned UV light absorber, can enumerate for example 2-(3,5-two-tertiary butyl-2-hydroxy phenyl)-benzotriazoles such as 5-chlorobenzotriazole are UV light absorber, 2-(4,6-phenylbenzene-1,3,5-triazine-2-yl)-and the 5-[(hexyl) oxidation]-triazines such as phenol are benzophenone series UV light absorber, 2 such as UV light absorber, eight benzophenone, 4-two-tert-butyl-phenyl-3, and the benzoic ether of 5-two-tertiary butyl-4-hydroxy benzoic ether etc. is a UV light absorber etc.
Above-mentioned antioxidant can be enumerated for example hindered phenol based compound, three azole compounds etc.Hindered phenol is an antioxidant, [3-(3 for example can to enumerate tetramethylolmethane-four, 5-two-tert-butyl-hydroxy phenyl) propionic ester], octadecyl-3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester], N, N '-hexane-1,6-two base is two, and [3-(3,5-two-tert-butyl-hydroxy phenyl propionic acid amide], phenylpropyl alcohol alkanoic acid 3, two (1, the 1-the dimethyl ethyl)-4-hydroxyl C7-C9 side chain alkyl esters, 2 of 5-, 4-dimethyl-6-(1-methyl pentadecyl) phenol etc.
As the said hydrolyzed stablizer, can enumerate as the aromatic series carbodiimide carbodiimide polymkeric substance that carbodiimide low-molecular(weight)polymer, the fusing point that about 40 ℃ carbodiimide monomer, the fusing point of especially preferred fusing point is 60～90 ℃ is 100～120 ℃.The above-mentioned relatively carbamate prepolymer of said hydrolyzed stablizer (A) 100 mass parts preferably cooperate with 0.01～3.0 mass parts, more preferably cooperate 0.1～2.0 mass parts.
As above-mentioned fire retardant, can cooperate nitrogenous compound, mineral compound etc. such as organic halogen based compound, phosphorus series compound, (different) tricyanic acid derivative compound.In addition, by the environment viewpoint preferred not halogen-containing fire retardant that cooperates that sets out.
It is bonding to use adhesive composite of the present invention to carry out the goods part.Goods are electrical apparatus product, for example can enumerate loudspeaker, cassette tape formula projector, TV, receiving set, vending machine, refrigerator, Personal Computer, CARD-BATTERY, Kamera etc. or camera from, also have auto parts and precision machinery etc. in addition.
[embodiment]
[embodiment]
Be described more specifically the present invention by the following examples, but these embodiment does not only do the explanation that limits for illustration.
Synthesizing of (synthesis example 1～3) carbamate prepolymer (A)
As table 1, after in possessing the stirrer of thermometer, adding the specified amount polyhydroxy reactant and carrying out processed, add the specified amount isocyanate prepolymer composition, under nitrogen environment, 70～90 ℃ of conditions, carry out reaction in 5 hours, obtain carbamate prepolymer A1～A3.The R value of the carbamate prepolymer of gained (ratio of NCO/OH) is shown in table 1 in the lump.
(relatively synthesis example 1 and 2) carbamate prepolymer X and Y's is synthetic
Except that change as making polyhydroxy reactant such as table 1, to obtain carbamate prepolymer X and Y with the same method of synthesis example 1～3.
[table 1]
Figure BDA0000070988040000081
Respectively cooperate the use level of material to represent in the table 1, * 1～* 6 as following with mass parts.
* 1) polytetramethylene glycol: hodogaya chemical industry (thigh) system, trade(brand)name PTG-2000, molecular weight 2000
* 2) modification polytetramethylene glycol: Asahi Chemical Industry's (thigh) system, trade(brand)name PTXG-L1800, molecular weight 1800
* 3) polycarbonate polyol: Asahi Chemical Industry's (thigh) system, trade(brand)name T5652, molecular weight 2000
* 4) polyester polyol: (thigh) Kuraray system, trade(brand)name Kuraray Polyol 2010, molecular weight 2000
* 5) polypropylene glycol: Mitsui Chemicals polyurethane(s) (thigh) system, trade(brand)name Diol 2000, molecular weight 2000
* 6) MDI: Japanese polyurethane industry (thigh) system, trade(brand)name millionate MT
(embodiment 1～14)
Cooperating shown in the table 2, after under nitrogen gas stream, the normal temperature carbamate prepolymer, silicon-dioxide and thinner being mixed, add curing catalysts, under nitrogen gas stream, under the normal temperature, mix, thereby obtain adhesive composite.
[table 2]
The embodiment numbering 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Prepolymer A1 100 - - 80 80 80 80 80 80 80 8O 80 - -
Prepolymer A2 - 100 - - - - - - - - - - 80 -
Prepolymer A3 - - 100 - - - - - - - - - - 80
Prepolymer x - - - 20 10 10 10 10 10 10 10 10 10 10
Prepolymer Y - - - - 10 10 10 10 10 10 10 10 10 10
Tertiary amine catalyst * 7 0.1 0.1 0.1 0.1 0.1 0.3 1.5 0.3 0.3 0.3 - - 0.3 0.3
Tin catalyst * 8 - - - - - - - - - - 0.1 1.0 - -
Silicon-dioxide * 9 - - - - - - - 1 10 20 10 10 10 10
Thinner * 10 20 20 20 20 20 20 20 20 20 20 20 20 20 20
Respectively cooperate the use level of material to represent in the table 2 with mass parts, prepolymer A1～A3 is respectively with 1～3 synthetic carbamate prepolymer of synthesis example A1～A3, prepolymer X and Y respectively do for oneself to compare synthesis example 1 and 2 synthetic carbamate prepolymer X and Y, * 7～* 10 as following.
* 7) amine is curing catalysts: two (morpholino ethyl) ether
* 8) tin is curing catalysts: day east changes into (thigh) system, trade(brand)name STANN BL, dioctyl tin two tertiary carbon acid esters
* 9) silicon-dioxide: Japanese Aerosil industry (thigh) system, trade(brand)name RY200S, pyrogenic silica
* 10) thinner: JAPAN ENERGY (thigh) system, trade(brand)name normal alkane N-11
Adhesive composite to above-mentioned gained carries out following test.Result such as table 3.
1. adhesive test
1-1) initial stage adhesive test
Test according to JISK6850.As by convered structure, use the polycarbonate (Mitsubishi's aerochemistry (thigh) system, trade(brand)name Iupiron sheet NF2000V) of 100 * 25 * 3mm.The thickness of adhesive composite about with 100 μ m is coated with, and open assembly time is made as after 5 minutes and fits.Then, will carry out the sample of 1 all slakings as initial stage adhesive test body with 23 ℃ of 50%RH.The assessment benchmark is as follows.
Zero: bonding strength 2.0N/mm 2More than and collapse state for showing the aggegation destructive sample of bond layer
△: bonding strength more than 1.0, do not reach 2.0N/mm 2Or collapse state is a sample of following the interfacial failure of bonding plane
*: bonding strength does not reach 1.0N/mm 2
1-2) heat-resistant fine adhesive function test
With initial stage adhesive test body in the drying machine of each temperature (100 ℃ or 130 ℃) with the slaking of specified time shown in the table 3 after, take out the test body, put cold 1 day test next day of carrying out with 23 ℃ of 50%RH.Test method is identical with the initial stage adhesive test.Calculate the strength retention shown in the following formula, and following commentary is estimated benchmark and is carried out heat-resistant fine adhesive function assessment.
Strength retention (%)=100 * (heat-resisting bonding strength/initial stage bonding strength)
◎: strength retention is more than 90%
Zero: strength retention more than 70%, do not reach 90%
△: strength retention more than 50%, do not reach 70%
*: strength retention does not reach 50%
2. operability test
According to the JISK6833 viscosity measurement, measure 23 ℃ viscosity of adhesive composite.Viscometer uses BS type viscometer, the viscosity when viscosity number uses rotation number 10rpm, and following commentary is estimated benchmark and is assessed.
◎: do not reach 200PaS
Zero: 200PaS is above, do not reach 400PaS
△: 400PaS is above, do not reach 600PaS
*: more than the 600PaS
The Ti value (BH type viscosity system 10rpm viscosity/1rpm viscosity) that to calculate by viscosimetric analysis as the fracture of wire index, estimate benchmark and assess by following commentary.
◎: the Ti value is more than 3.0
Zero: Ti value more than 2.0, do not reach 3.0
△: Ti value more than 1.5, do not reach 2.0
*: the Ti value does not reach 1.5
3. solidified nature test
Adhesive composite evenly being coated with about with thickness 3mm on the release paper under 23 ℃ of 50%RH, measure the time till making film.The assessment benchmark is as follows.
◎: the time till making film does not reach 10 minutes
Zero: time till making film more than 10 minutes, do not reach 40 minutes
△: time till making film more than 40 minutes, do not reach 80 minutes
*: the time till making film is more than 80 minutes
4. storage stability test
The viscosity that the aforesaid operations test is measured moves to encloses container to sample as initial value, 50 ℃ carry out heating in 1 week after, 23 ℃ carry out putting in 1st cold after, with the viscosity measurement of JISK6833, carry out viscosimetric analysis.Calculate tackify rate (measured value/initial value), and following commentary is estimated benchmark and is assessed.
Zero: the tackify rate does not reach 1.5
△: the tackify rate is more than 1.5～do not reach 2.0
*: the tackify rate is more than 2.0
[table 3]
As shown in table 3, adhesive composite of the present invention is good to the initial stage cementability and the heat-resistant fine adhesive function of polycarbonate, and operability, solidified nature and stability in storage excellence.
(comparative example 1 and 2)
Except that as table 4, changing composition, obtain adhesive composite with similarly to Example 1 method.The adhesive composite that makes gained is tested similarly to Example 1.Result such as table 5.
[table 4]
Comparative example 1 Comparative example 2
Prepolymer-X 100 -
Prepolymer-Y - 100
Tertiary amine catalyst * 7 0.3 0.3
Silicon-dioxide * 9 10 10
Thinner * 10 20 20
In the table 4, each cooperates the use level of material to represent with mass parts, and prepolymer X and Y are respectively with synthesis example 1 relatively and 2 synthetic carbamate prepolymer X and Y, and * 7, * 9 and * 10 are with table 2.
(comparative example 3)
Using modified silicone is that caking agent (trade(brand)name 1530, ThreeBond (thigh) system) is tested similarly to Example 1.Result such as table 5.
(comparative example 4)
(polypropylene glycol-MDI) is caking agent (trade(brand)name UM600V, Cemedine (thigh) make), tests similarly to Example 1 to use carbamate.Result such as table 5.
[table 5]
Figure BDA0000070988040000151

Claims (3)

1. thermotolerance one a liquid moisture-curable polycarbonate resin adhesive composite is characterized in that, it is to engage polycarbonate resin polycarbonate resin adhesive composite each other,
The end that contains the polyvalent alcohol more than a kind that is selected from polytetramethylene glycol, modification polytetramethylene glycol and the polycarbonate polyol and polyisocyanates reaction gained have the carbamate prepolymer (A) of isocyanate group and be selected from tertiary amine catalyst and tin catalyst in the curing catalysts more than a kind (B).
2. thermotolerance one liquid moisture-curable polycarbonate resin adhesive composite as claimed in claim 1 wherein, also contains silicon-dioxide (C).
3. thermotolerance one liquid moisture-curable polycarbonate resin adhesive composite as claimed in claim 1 or 2, wherein, above-mentioned relatively carbamate prepolymer (A) 100 mass parts cooperate above-mentioned curing catalysts (B) 0.01～10 mass parts.
CN2009801525076A 2009-01-29 2009-10-02 Heat-resistant moisture-curable adhesive composition for polycarbonate resin Pending CN102264857A (en)

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