CN105051134A - Adhesives and related methods - Google Patents

Adhesives and related methods Download PDF

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CN105051134A
CN105051134A CN201380063171.2A CN201380063171A CN105051134A CN 105051134 A CN105051134 A CN 105051134A CN 201380063171 A CN201380063171 A CN 201380063171A CN 105051134 A CN105051134 A CN 105051134A
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agent
theme
component
vinylformic acid
composition
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CN105051134B (en
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M·扎加奇科夫斯基
M·T·沃特曼
K·R·海姆贝奇
E·L·巴塞洛缪
B·S·米勒
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Avery Dennison Corp
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Avery Dennison Corp
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Priority to CN201910338343.1A priority Critical patent/CN110079218B/en
Priority claimed from PCT/US2013/064188 external-priority patent/WO2014059056A1/en
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Abstract

Cure in place pressure sensitive adhesive compositions are described that comprise one or more of a bodying component, a structural diluent, a radical diluent as well as additives such as crosslinkers, external catalysts, photoinitiators and stabilizers/ process aids. The bodying component can be acrylic or non-acrylic.

Description

Sizing agent and methods involving
The cross reference of related application
This application claims the right of priority of the U.S.Provisional Serial 61/711,386 being filed on October 9th, 2012.
Technical field
This theme relates generally to and the reactive oligomers of acrylate or the blending of ethylene-propylene perester radical plinth polymkeric substance and/or compound.In some form, non-acrylate polymers is used in blend.This blend produces the potential functionality that comprises on oligopolymer and/or the pressure-sensitive adhesive agent (PSA) for suitably crosslinked additive.Crosslinked by surface catalysis, UV irradiation or the triggering of other curing mechanisms.
Specifically, this theme relates to pressure-sensitive adhesive agent composition, relates more specifically in wide temperature range, have high fusible pressure-sensitive adhesive agent.This theme also relates to suitable solidified liquid composition.This theme also relates to formation method and uses the method for this composition.This theme relates to the foam article being incorporated to said composition further.
Summary of the invention
This theme relates generally to the pressure-sensitive adhesive agent of suitably being solidified by UV light, surface catalysis or some other mechanism, and it obtains the intensity more much higher than typical PSA.This sizing agent is formed by reactive oligomers and one or more high-molecular-weight propylene acid ester polymer blending usually.An example is the blend of the acrylate copolymer of silane-functional and the polyethers of silyl end-blocking.This blend is inherent viscosity, and is cured by this blend is exposed to the compound comprising oligomeric silane, and described oligomeric silane such as can be printed on matching surface.
In one embodiment, the pressure-sensitive adhesive agent of this theme or the composition of suitably solidification are formed by comprising following blend: (a) reactive oligomers and (b) high-molecular-weight propylene acid ester polymer.This blend is inherent viscosity, and is cured by this blend is exposed to the compound comprising oligomeric silane, and described oligomeric silane can be introduced on the surface by being printed on.
The another kind of embodiment of this theme is the pressure-sensitive adhesive agent of suitably solidification, it comprises: the multiviscosisty component (bodyingcomponent) of (a) 20-80 weight percentage (wt%), it comprises and has 5, 000 to 1, 000, 000, be 15 in some embodiments, 000-250, 000, with be 15 in still other embodiments, 000-100, the vinylformic acid base polymer of the molecular weight (Mw) of 000, one or more structure thinners of (b) 5-50wt%, one or more free radical addition thinners of (c) 10-80wt%, one or more linking agents of (d) 0-4.0wt%, one or more external catalysts of (e) 0-4.0wt%, one or more photoinitiators of (f) 0.01-10wt%, (g) one or more stablizer/processing aids of 0-10.0wt%.
The another kind of again embodiment of this theme is the pressure-sensitive adhesive agent of suitably solidification, it comprises the multiviscosisty component of (a) 20-80wt%, it comprises and has 1, 000 to 500, 000, be 1 in some embodiments, 000-100, 000, with be 1000-50 in still other embodiments, the base polymer of the Mw of 000, described base polymer is selected from polyolefine, polyvinyl aromatic hydrocarbon, urethane, polycarbonate, polyester, polyethers and its combination, one or more structure thinners of (b) 5-50wt%, one or more free radical addition thinners of (c) 10-80wt%, one or more linking agents of (d) 0-1.0wt%, one or more external catalysts of (e) 0-4.0wt%, one or more photoinitiators of (f) 0.01-10wt%, (g) one or more stablizer/processing aids of 0-10.0wt%.
The other embodiment of this theme comprises the pressure-sensitive adhesive agent of suitably solidification, it comprises: (a) 20-80wt% has 100,000 to 1,000,000 and be 250 in some embodiments, 000-750, the vinylformic acid base polymer of the Mw of 000, one or more tackifier of (b) 0-30wt%, one or more liquid reactions components of (c) 5-40wt%, vinylformic acid-epoxy functionalized the component of (d) 0-30wt% and/or epoxy functionalized alkene, and the metal chelate crosslinMng agent-catalyzer of (e) 0-2wt% and/or external catalyst.
The other embodiment of this theme comprises the pressure-sensitive adhesive agent of suitably solidification, it comprises: (a) 50-80wt% has 250,000-750, the vinylformic acid base polymer of the Mw of 000, one or more structure thinners of (b) 10-30wt%, the metal chelate crosslinMng agent of (c) 0-0.5wt%, one or more external catalysts of (d) 0-2wt%, and the stablizer/processing aid of (e) 0-10wt%.
The other embodiment of this theme comprises the pressure-sensitive adhesive agent of suitably solidification, it comprises: (a) 50-80wt% has 250,000-750, the vinylformic acid base polymer of the Mw of 000, one or more structure thinners of (b) 20-40wt%, optional vinylformic acid-epoxy functionalized the component of (c) 0-30wt%, the metal chelate crosslinMng agent of (d) 0-0.5wt%, one or more external catalysts of (e) 0-2wt%, and the stablizer/processing aid of (f) 0-10wt%.
The other embodiment of this theme comprises the liquid of suitably solidification, it comprises: the multiviscosisty component of (a) 5-70wt%, it comprises and has 5, 000 to 1, 000, 000, be 15 in some embodiments, 000-250, 000, with be 15 in still other embodiments, 000-100, the vinylformic acid base polymer of the Mw of 000, one or more structure thinners of (b) 5-40wt%, one or more free radical addition thinners of (c) 30-95wt%, one or more external catalysts of (d) 0-10.0wt%, one or more photoinitiators of (e) 0-10wt%, one or more photosensitizerss of (f) 0-10wt%, (g) stablizer (one or more) of 0-10wt%.
The other embodiment of this theme comprises the liquid of suitably solidification, it comprises: the multiviscosisty component of (a) 5-50wt%, it comprises and has 15,000 to 100, the vinylformic acid base polymer of the Mw of 000, one or more structure thinners of (b) 50-95wt%, one or more external catalysts of (c) 0.01-10wt%, and the stablizer/processing aid of (d) 0-10wt%.
The other embodiment of this theme comprises the liquid of suitably solidification, it comprises the multiviscosisty component of (a) 30-70wt%, it comprises and has 15,000-100, the acrylic copolymer of the Mw of 000, one or more structure thinners of (b) 7-70wt%, one or more free radical addition thinners of (c) 7-70wt%, one or more photoinitiators of (d) 2-10wt%, one or more antioxidants of (e) 0-1%, and the stablizer/processing aid of (f) 0-10wt%.
The other embodiment of this theme comprises the liquid of suitably solidification, it comprises: the multiviscosisty component of (a) 5-70wt%, it comprises and has 5, 000 to 1, 000, 000, be 15 in some embodiments, 000-250, 000, with be 15 in still other embodiments, 000-100, the vinylformic acid base polymer of the Mw of 000, one or more structure thinners of (b) 5-80wt%, one or more free radical addition thinners of (c) 5-70wt%, one or more external catalysts of (d) 0-5.0wt%, one or more photoinitiators of (e) 0-10wt%, one or more photosensitizerss of (f) 0-10wt%, (g) stablizer/processing aid of 0-10wt%.
The other embodiment of this theme comprises the liquid of suitably solidification, it comprises: the multiviscosisty component of (a) 10-15wt%, it comprises and has 15, 000-100, the vinylformic acid base polymer of the Mw of 000, one or more structure thinners of (b) 45-60wt%, one or more free radical addition thinners of (c) 30-40wt%, one or more external catalysts of (d) 0.01-2.0wt%, the photoinitiator of (e) 0.01-10wt%, one or more photosensitizerss of (f) 0-10wt%, (g) stablizer/processing aid of 0-10wt%.
The other embodiment of this theme comprises the liquid of suitably solidification, it comprises: the multiviscosisty component of (a) 5-70wt%, it comprises and has 1, 000 to 500, 000, be 1 in some embodiments, 000-100, 000, with be 1 in still other embodiments, 000-50, the non-vinylformic acid base polymer of the Mw of 000, described non-vinylformic acid base polymer is selected from polyolefine, polyvinyl aromatic hydrocarbon, urethane, polycarbonate, polyester, polyethers and its combination, one or more structure thinners of (b) 5-80wt%, one or more free radical addition thinners of (c) 0-40wt%, one or more external catalysts of (d) 0-5.0wt%, one or more photoinitiators of (e) 0-10wt%, one or more photosensitizerss of (f) 0-10wt%, (g) stablizer/processing aid of 0-10wt%.
The other embodiment of this theme comprises the liquid of suitably solidification, it comprises: the multiviscosisty component of (a) 5-50wt%, it comprises and has 5,000 to 1,000,000 and in some embodiments 15, the non-acrylate copolymer of 000-100, the Mw of 000, one or more structure thinners of (b) 50-95wt%, one or more external catalysts of (c) 0.01-10wt%, and the stablizer/processing aid of (d) 0-10wt%.Described non-acrylate copolymer is selected from polyolefine, polyvinyl aromatic hydrocarbon, urethane, polycarbonate, polyester, polyethers and its combination.
The other embodiment of this theme comprises the liquid of suitably solidification, it comprises: the multiviscosisty component of (a) 5-70wt%, it comprises and has 1, 000 to 500, 000, be 1 in some embodiments, 000-100, 000, with be 1 in still other embodiments, 000-50, the non-vinylformic acid base polymer of the Mw of 000, described non-vinylformic acid base polymer is selected from polyolefine, polyvinyl aromatic hydrocarbon, urethane, polycarbonate, polyester, polyethers and its combination, one or more structure thinners of (b) 5-80wt%, one or more free radical addition thinners of (c) 5-70wt%, one or more external catalysts of (d) 0-5.0wt%, one or more photoinitiators of (e) 0-10wt%, one or more photosensitizerss of (f) 0-10wt%, (g) stablizer/processing aid of 0-10wt%.
The other embodiment of this theme comprises the liquid of suitably solidification, it comprises: the multiviscosisty component of (a) 10-15wt%, it comprises and has 1, 000 to 500, 000, be 1 in some embodiments, 000-100, 000, with be 1 in still other embodiments, 000-50, the non-acrylate copolymer of the Mw of 000, one or more structure thinners of (b) 45-60wt%, one or more free radical addition thinners of (c) 30-40wt%, one or more external catalysts of (d) 0.01-2.0wt%, one or more photoinitiators of (e) 0.01-10wt%, one or more photosensitizerss of (f) 0-10wt%, (g) stablizer/processing aid of 0-10wt%.Described non-acrylate copolymer is selected from polyolefine, polyvinyl aromatic hydrocarbon, urethane, polycarbonate, polyester, polyethers and its combination.
The other embodiment of this theme comprises the liquid of suitably solidification, it comprises: the multiviscosisty component of (a) 5-70wt%, it comprises and has 5, 000 to 1, 000, 000, be 15 in some embodiments, 000-250, 000, with be 15 in still other embodiments, 000-100, the vinylformic acid base polymer of the Mw of 000, the multiviscosisty component of (b) 5-70wt%, it comprises and has 1, 000 to 500, 000, be 1 in some embodiments, 000-100, 000, with be 1 in still other embodiments, 000-50, the non-vinylformic acid base polymer of the Mw of 000, described non-vinylformic acid base polymer is selected from polyolefine, polyvinyl aromatic hydrocarbon, urethane, polycarbonate, polyester, polyethers and its combination, one or more structure thinners of (c) 5-80wt%, one or more free radical addition thinners of (d) 0-40wt%, one or more external catalysts of (e) 0-5.0wt%, one or more photoinitiators of (f) 0-10wt%, one or more photosensitizerss of (g) 0-10wt%, (h) stablizer/processing aid of 0-10wt%.
The other embodiment of this theme comprises the liquid of suitably solidification, it comprises: the multiviscosisty component of (a) 5-50wt%, it comprises and has 5, 000 to 1, 000, 000, be 15 in some embodiments, 000-250, 000, with be 15 in still other embodiments, 000-100, the vinylformic acid base polymer of the Mw of 000, the multiviscosisty component of (b) 5-50wt%, it comprises and has 1, 000 to 500, 000, be 1 in some embodiments, 000 to 50, the non-vinylformic acid base polymer of the Mw of 000, described non-vinylformic acid base polymer is selected from polyolefine, polyvinyl aromatic hydrocarbon, urethane, polycarbonate, polyester, polyethers and its combination, one or more structure thinners of (c) 50-95wt%, one or more external catalysts of (d) 0.01-10wt%, one or more photosensitizerss of (e) 0-10wt%, (f) stablizer/processing aid of 0-10wt%.
The other embodiment of this theme comprises the liquid of suitably solidification, it comprises: the multiviscosisty component of (a) 70-80 weight percentage, it comprises and has 15,000-250,000 and be 18,000 – 70 in some embodiments, the acrylic copolymer of the Mw of 000, one or more structure thinners of (b) 15-20wt%, one or more photoinitiators of (c) 0.01-5wt%, and the stablizer/processing aid of (d) 0-10wt%.
The other embodiment of this theme comprises the liquid of suitably solidification, it comprises: the multiviscosisty component of (a) 5-15wt%, it comprises and has 5, 000 to 1, 000, 000, be 15 in some embodiments, 000-250, 000, with be 15 in still other embodiments, 000-100, the vinylformic acid base polymer of the Mw of 000, the multiviscosisty component of (b) 5-15wt%, it comprises and has 1, 000 to 500, 000, be 1 in some embodiments, 000-100, 000, with be 1 in still other embodiments, 000-50, the non-vinylformic acid base polymer of the Mw of 000, described non-vinylformic acid base polymer is selected from polyolefine, polyvinyl aromatic hydrocarbon, urethane, polycarbonate, polyester, polyethers and its combination, one or more structure thinners of (c) 45-60wt%, one or more free radical addition thinners of (d) 30-40wt%, one or more external catalysts of (e) 0.01-2.0wt%, one or more photoinitiators of (f) 0.01-10wt%, one or more photosensitizerss of (g) 0-10wt%, (h) stablizer/processing aid of 0-10wt%.
The other embodiment of this theme comprises the liquid of suitably solidification.This liquid comprises the multiviscosisty component of (a) 5-70wt%, it comprises and has 5,000 to 1,000, the non-vinylformic acid base polymer of the Mw of 000, described non-vinylformic acid base polymer is selected from polyolefine, polyvinyl aromatic hydrocarbon, urethane, polycarbonate, polyester, polyethers and its combination; At least one structure thinner of (b) 0-40wt%; At least one free radical addition thinner of (c) 30-95wt%; The solidifying agent of (d) 0-10.0wt%; The photosensitizers of (e) 0-10wt%; (f) stablizer of 0-10wt%.
The another kind of embodiment of this theme comprises the method that solidified pressure-sensitive sticks agent.Specifically, the method that solidified pressure-sensitive sticks agent comprises the pressure-sensitive adhesive agent providing suitably solidification, described pressure-sensitive adhesive agent comprises the multiviscosisty component of 20-80wt%, it comprises and has 5,000 to 1,000, the vinylformic acid base polymer of the Mw of 000, the at least one structure thinner of 5-50wt%, the at least one free radical addition thinner of 10-80wt%, the linking agent of 0-10.0wt%, first solidifying agent of 0-4.0wt%, second solidifying agent of 0.01-10wt%, and the stablizer/processing aid of 0-10.0wt%.The method also comprises makes sizing agent expose or experience is selected from radiation, heat, moisture, pressure, first the stimulating of ultrasonic, Chemical exposure and its combination.
The another kind of embodiment of this theme comprises the pressure-sensitive adhesive agent of suitably solidification, and what it comprised (a) 50-80wt% has 250,000-750, the vinylformic acid base polymer of the Mw of 000; At least one structure thinner of (b) 10-30wt%; At least one metal chelate crosslinMng agent of (c) 0-0.5wt%; The solidifying agent of (d) 0-2wt%; (e) stablizer/processing aid of 0.1-10wt%.
As will be recognized, theme as herein described can realize other and different embodiments, and its some details can carry out the improvement of all respects, and it does not all deviate from claimed theme.Therefore, drawing and description are considered to schematic and are not restrictive.
Accompanying drawing explanation
Fig. 1 depicts the dynamic mechanical analysis of some embodiment of the pressure-sensitive adhesive agent of suitably solidification in embodiment 3.
Fig. 2 depicts the general adhesive method of this theme.
Fig. 3 depicts the program of lap shear test (LapShearTest) of embodiment 34.
Fig. 4 depicts the program of the lap shear test of embodiment 35.
Fig. 5 depicts and applies liquid to substrate with subsequently by being exposed to the schematic diagram of the suitable solidified liquid of actinic radiation.
Fig. 6 describes the indicative flowchart according to the adhesive method of this theme.
Detailed Description Of The Invention
In some embodiments, the sizing agent of the suitable solidification of this theme comprises (i) multiviscosisty component, that it can be acrylic or non-acrylic or comprise acrylate and non-acrylate combination, (ii) one or more structure thinners, (iii) one or more free radical addition thinners, (iv) one or more additives, such as (a) linking agent, (b) catalyzer such as thermocatalyst and alkaline catalysts, (c) photoinitiator, it comprises free radical photoinitiator, UV free radical photoinitiator and I and II type photoinitiator, d () comprises the photosensitizers of dyestuff, (e) stablizer or processing aid.The general introduction of the selection of visible three kinds of main ingredients (i)-(iii) in following table 1.
Table 1: the exemplary lists of the main ingredient of composition
There is provided herein the details of these different componentss.
Multiviscosisty component
Broadly define multiviscosisty component herein for having at least 25,000 daltonian molecular weight (Mw).Multiviscosisty component (one or more) can with 10-90wt%, be 20-80wt% in some embodiments, with be 30-70wt% in still other embodiments, 5-70wt% alternatively, 40-60wt% alternatively, alternatively 30-50wt%, alternatively 5-15wt%, 10-15wt% alternatively, or the amount of 80wt% is present in the composition of this theme.Multiviscosisty component can be the multiviscosisty component of acrylic or the multiviscosisty component of non-acrylic.Can use these and potentially with the combination of other components.Multiviscosisty component can have 5,000 to 1, and 000,000, be 15,000-250 in some embodiments, 000, and be 15 in still other embodiments, 000-100,000, alternatively 1,000 to 500,000, be 1,000-100 in some form, 000, with be 1,000-50 in still other forms, 000, or alternatively 18,000-70,000 molecular weight (Mw).
In some embodiment of this theme, the multiviscosisty component of concrete acrylic can use as follows.Should be appreciated that this theme comprises alternative any acrylate monomer, oligopolymer or component pointed out, or in addition, use corresponding methacrylate monomer, oligopolymer or component.
MJZ4-87-1: multiviscosisty component.This multiviscosisty component is by the Additol of the vinyl-acetic ester of the 2-EHA of 55wt%, 25wt%, the methyl acrylate of 18wt% and 2wt% tMthe atactic propene acid copolymer of the number-average molecular weight (Mn) (heterogeneity index (PDI) 3.5, random copolymers) with 50k of S-100 composition.
MW1-65: multiviscosisty component.This multiviscosisty component is by the Additol of the 2-EHA of 50wt%, the methyl acrylate of 48wt% and 2wt% tMthe atactic propene acid copolymer of the Mn (PDI3.5, random copolymers) with 50k of S-100 composition.
MW1-69: multiviscosisty component.This multiviscosisty component is the Elvacite of methyl acrylate 43.1% by the 2-EHA of 44.9wt%, 43.1wt%, 10.2wt% tMthe Additol of 1020 (pMMA) and 1.8wt% tMthe atactic propene acid copolymer of the Mn (PDI3.5, random copolymers) with 50k of S-100 composition.
MW1-91: multiviscosisty component.The atactic propene acid copolymer of the Mn (PDI3.5, random copolymers) with 50k that this multiviscosisty component is made up of the 2-EHA of 56.1wt%, the vinyl-acetic ester of 25.5wt%, the methyl acrylate of 18.4wt%.
MW1-93 (most preferred embodiment of synthesis is MW1-101).The atactic propene acid copolymer of the Mn (PDI3.5, random copolymers) with 50k that this multiviscosisty component is made up of the 2-EHA of 55wt%, the vinyl-acetic ester of 25wt%, the methyl acrylate of 18wt%, the glycidyl ethacrylate of 2wt%.
MW1-94: multiviscosisty component.This multiviscosisty component is the adducts of vinylformic acid and MW1-93, and it comprises glycidyl methacrylate and chromium (3+) catalyzer of MW1-93 and 2wt% of 98wt%.
The Detailed composition of some the multiviscosisty component presented in Table 1 is illustrated in following table 2.
Abbreviation in aforementioned table 2 comprises: BA: butyl acrylate; 2-EHA: 2-EHA; TBA: tert. butylacrylate; EOEOEA: ethoxyethoxy ethyl acrylate; PPO: polyoxytrimethylene, BMA: butyl methacrylate.
Free radical addition thinner
Free radical addition thinner has to be generally less than 25, the molecular weight (Mw) of 000 and/or the monomer generally had lower than the acrylic of the viscosity of 25,000cps at 25 DEG C.Free radical addition thinner is herein sometimes referred to as reactive diluent.Free radical addition thinner, with 10-80wt%, is 50-70wt%, alternatively 10-60wt% in some embodiments, 5-70wt% alternatively, 0-40wt% is alternatively 30-40wt% in still other embodiments, or the amount of 7-25wt% is alternatively present in the composition of this theme.Free radical addition thinner can comprise (methyl) acrylate monomer and have in some form and is less than 10,000 daltonian total Mw.The example of free radical addition thinner useful herein comprises ACE, isooctadecanol acrylate, vinylformic acid heptadecyl ester, vinylformic acid Dicyclopentadiene (DCPD) ester, THF acrylate, alkoxylate THF acrylate, Hydroxyethyl acrylate, acrylate, urethaneacrylates (Mw<2000), OXE-10, OXE-30, S-100, V2100, alicyclic V2100 and PAMA.Be described in more detail in these components in conjunction with example herein many.Below the example of some free radical addition thinners is illustrated in detail.
Alkoxylate THF acrylate can be used as the low viscosity monofunctional monomer of CD-611 acquisition from Sartomer, and wherein n is open, and it is shown as formula (1) as follows:
Hydroxyethyl acrylate: this free radical addition thinner is shown as formula (2) as follows:
Acrylate: this free radical addition thinner is shown as formula (3) as follows:
This low viscosity monofunctional monomer can be used as SR339 and obtains from Sartomer.
Vinylformic acid tetrahydrofuran ester (THFA or THF acrylate): this free radical addition thinner is shown as formula (4) as follows.This low viscosity monofunctional monomer can be used as SR285 and obtains from Sartomer.
Structure thinner can be present in the composition of this theme with amount below: 5-80wt%, alternatively 5-50wt%, is 10-50wt% in some embodiments, 5-40wt% alternatively, 10-30wt% alternatively, alternatively 20-40wt%, alternatively 65-95wt%, 75-85wt% alternatively, 75-95wt% alternatively, alternatively 7-25wt%, alternatively 45-65wt%, 45-60wt% alternatively, 75-85wt% and alternatively 15-20wt% alternatively.Structure thinner is herein sometimes referred to as structural constituent.In conjunction with embodiment herein, various structure thinner and details are described.
Various structure thinner comprises following: Viscoat 295 (TMPTA).This monomer can be used as SR351 and obtains from Sartomer, and is shown as formula (5) as follows:
Tri (propylene glycol) diacrylate, can be used as SR306 and obtains from Sartomer, and be shown as formula (6) as follows:
Ethoxylation (3mol) bisphenol a diacrylate.This monomer can be used as SR349 and obtains from Sartomer, wherein n+m=3, and is shown as formula (7) as follows:
Ethoxylation (3mol) Viscoat 295, and be shown as formula (8) as follows:
This monomer can be used as SR454 and obtains from Sartomer.
Bisphenol A diglycidyl ether diacrylate is shown as formula (9) as follows:
This monomer can be used as Ebecryl600 and obtains from Cytec.
Radical structure component comprises one or more curable materials, and it comprises the homopolymer with Tg>0 DEG C.This applicable component comprises Viscoat 295 (TMPTA), ethoxylation (xmol) bisphenol a diacrylate, ethoxylation (xmol) Viscoat 295 and bisphenol A diglycidyl ether diacrylate.This value x is from 1 to 10, is from 1 to 5 in some embodiments, and is 3 in still other embodiments.
Open loop structure component also can be used in some embodiment.Be applicable to open loop structure component comprise S-21, S-28, Epon828, Epon834, a-186 and a-187.Also useful is epoxy, trimethylene oxide, acid anhydride and lactan.
The monomer of cationically polymerizable comprises the material, alkyl vinyl ether, cyclic ethers, vinylbenzene, Vinylstyrene, Vinyl toluene, N-vinyl compound, 1-alkyl alkene (alpha-olefin), lactan and the cyclic acetal that comprise epoxy.
The material comprising epoxy that is curable by the catalysis system of this theme or polymerization is those of known experience cationoid polymerisation, and comprises 1,2-cyclic ethers, 1,3-cyclic ethers and Isosorbide-5-Nitrae-cyclic ethers (also called after 1,2-epoxide, 1,3-epoxide and Isosorbide-5-Nitrae-epoxide).1,2-cyclic ethers is used to some form of this theme.
Be included in Frisch and Reegan, Ring-OpeningPolymerizations according to the polymerisable cyclic ethers of this theme, describe in volume Two (1969) those.1, the 2-cyclic ethers be applicable to is the epoxide of monomer and aggretion type.They can be aliphatics, alicyclic, aromatics or heterocycle, and by usually have from 1 to 6 and be in some embodiments 1 to 3 epoxy equivalent (weight).What be particularly useful is aliphatics, alicyclic and diglycidyl ether type 1, 2-epoxide, such as propylene oxide, Epicholorohydrin, Styrene oxide 98min., vinylcyclohexene oxygen, vinyl cyclohexene dioxide, Racemic glycidol, oxygenated butadiene, the glycidyl ether of dihydroxyphenyl propane, cyclohexene oxide, 3, 4-epoxycyclohexyl-methyl-3, 4-epoxycyclohexane carboxylate, 3, 4-epoxy-6-methylcyclohexylmethyl-3, 4-epoxy-6-methylcyclohexanecarboxylic acid ester, two (3, 4-epoxy-6-methylcyclohexylmethyl) hexanodioic acid, bicyclopentadiene dioxide, epoxidized polybutadiene, 1, 4-butanediol diglycidyl ether, the polyglycidyl ether of phenol formaldehyde resole or novolac resin, resorcinol diglycidyl ether and epoxysilicone, such as, there is the dimethyl siloxane of cycloaliphatic epoxides or glycidyl ether group.
Various commercial epoxy resin is available and at Lee and Neville, HandbookofEpoxyResins, (1967) and at P.Bruins, EpoxyResinTechnology, lists in (1968).Trimethylene oxide, 3,3-two (chloromethyl) trimethylene oxide and tetrahydrofuran (THF)s according to this theme polymerisable representative 1,3-and Isosorbide-5-Nitrae-cyclic ethers.
Especially, the cyclic ethers easily obtained comprises propylene oxide, trimethylene oxide, Epicholorohydrin, tetrahydrofuran (THF), Styrene oxide 98min., cyclohexene oxide, vinylcyclohexene oxygen, Racemic glycidol, octylene oxide, phenyl glycidyl ether, 1,2-is oxidized butane, the glycidyl ether (such as, Epon828 and DER331) of dihydroxyphenyl propane, vinyl cyclohexene dioxide (such as, ERL-4206), 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate (such as, ERL-4221), 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylic acid ester (such as ERL-4201), two (3,4-epoxy-6-methylcyclohexylmethyl) hexanodioic acid (such as, ERL-4299), the aliphatic epoxy resin (such as, ERL-4050 and ERL-4052) of polypropylene glycol modified, Dipentenedioxide (such as, ERL-4269), epoxidized polybutadiene (such as, Oxiron2001), silicone epoxy (such as, Syl-Kem90), BDDE (such as, AralditeRD-2), the polyglycidyl ether (such as, DER-431) of formaldehyde phenolic resin varnish, Epi-Rez521 and DER-438), resorcinol diglycidyl ether (such as, Kopoxite), polyglycol diepoxide (such as, DER-736), polyacrylic ester epoxide (such as, EpocrylU-14), urethane-modified epoxide (such as, QX3599), multifunctional flexible epoxies (such as, Flexibilizer151), with its mixture, and itself and also know help solidifying agent, the mixture (Lee and Neville seen above and Bruins) of solidifying agent or stiffening agent.The solidifying agent that helps of spendable representational stiffening agent is acid anhydrides such as methylnadic anhydride, pentamethylene tetracarboxylic dianhydride, pyromellitic anhydride, cis-1,2-cyclohexane dicarboxylic acid acid anhydrides and its mixture.
The monomer that can be used for the cationically polymerizable of this theme includes but not limited to comprise the material of epoxy, alkyl vinyl ether, cyclic ethers, vinylbenzene, Vinylstyrene, Vinyl toluene, N-vinyl compound, cyanate, 1-alkene (alhpa olefin), lactan and cyclic acetal.
At U.S. Patent number 5,252,694 the 4th hurdles the 30th walk to the 5th hurdle the 34th line description monomer of other cationically polymerizable.The concrete monomer of the type comprises 828, and the ERL series of 1001F and cycloaliphatic epoxy monomer such as or the monomer be particularly useful is ERL series, because their lower solidification values.
Some lactone can be used for this theme.The lactone that can be used as comonomer in this theme comprises following those of formula (10)-(12) of being shown as:
Wherein n be 4 or 5, h, i, k and m be 1 or 2 independently, and each R is independently selected from H or the alkyl comprising 12 carbon atoms at the most.Concrete lactone is that wherein R is those of hydrogen or methyl, the lactone be particularly useful in some embodiments is e-caprolactone, d-valerolactone, glycollide (Isosorbide-5-Nitrae-dioxane-2,5-diketone), 1,5-Dioxepane-2-ketone and Isosorbide-5-Nitrae-dioxane-2-ketone.
The thinner that can be used for the other type of this theme is ring-opened monomer thinner.Under the condition of the radical polymerization adopted, also right and wrong are reactive for this thinner and other reactants, and its can form acrylic ester polymer during curing schedule after through going through open loop.This open loop thinner includes but not limited to lactone, lactan, cyclic ethers and cyclosiloxane that the following general formula by being shown as (13)-(16) as follows represents:
In formula (13)-(16), x scope from such as 3 to 11, and in some form 3-6 alkylidene group.
U.S. Patent number 5,082,922 describe ring-opened monomer as thinner for from the solvent-free formation polymkeric substance of ethylenically unsaturated monomers.But, that patent describes the one-step reaction of monomer together with open loop thinner.This is different from the two-step Taylor-Galerkin of some method of this theme, and it provides polymkeric substance from the initial formation of ethylenically unsaturated monomers, solidifies thinner subsequently when there is the polymkeric substance therefore formed.The patent mentioned provides the use of the temperature of reaction conditions such as at least 150 DEG C, and it supports two reactions in single step.
Useful ring-opened monomer thinner includes but not limited to butyrolactone, valerolactone, caprolactone, methyl-butyrolactone, butyrolactam, Valerolactim, hexanolactam and siloxanes.
A kind of siloxanes ring-opened monomer is a-186, it serves as the structural constituent of curing reaction structural constituent and silane-functional by silane-silane condensation reaction. a-186 (β (3,4-epoxycyclohexyl) ethyl trimethoxy silane) has following formula (17):
Although polyreaction can be carried out when there is non-reactive solvent, this reaction advantageously can occur in substantially solvent-free situation.In some embodiments, solvent will with by weight at the most about percent 10, and the amount being preferably not more than by weight percent 5 exists, and this is based on the gross weight of reactant.Solvent can be removed from the product of thinner reactions steps (as by heating).Exemplary non-reactive solvent comprises ketone, alcohols, ester class and hydrocarbon solvent, such as ethyl acetate, toluene and dimethylbenzene.
For this theme azoles quinoline or azoles alkane comprises those with following formula (18)-(19):
Wherein R represents that comprise the branching of 5 to 8 carbon, saturated aliphatic alkyl.Another is applicable to azoles woods is shown as (20) as follows:
Wherein R represents that comprise the branching of 5 to 8 carbon, saturated aliphatic alkyl.
Useful herein azoles alkylating mixture is less than 8,000mPa.s at usually having 23 DEG C, and is less than the viscosity of 6,500mPa.s in some form, therefore, is suitable as the solvent-free stiffening agent of the polymer precursor comprising isocyanate groups.With the polymer precursor composition comprising isocyanate groups, they are suitable for the production of solvent-free or low solvent, one-component system, and it is suitable as again the sizing agent of high quality mould coating, coating composition or sealing compositions.These systems are cured after the application by being exposed to atmospheric moisture usually.The polymer precursor comprising isocyanate groups being suitable for producing these systems is included in such as U.S. Patent number 4,002, the organic polyisocyanates described in 601 or isocyanate prepolymer.Usually, at U.S. Patent number 5,189, describe useful in 176 herein azoles quinoline.
In some embodiments, bismaleimides can be used.The bismaleimides that can be used for this theme is the organic compound comprising two maleimide base groups, and is generally prepared by maleic anhydride and diamine.By following general formula (21), bismaleimides can be described:
Wherein R 3divalent aromatic or alicyclic organic group.In some form, useful bismaleimides is derived from aromatic diamine, and especially wherein R 3those of polynuclear aromatic base.The example of this bismaleimides comprises 2, two (4-amino-benzene oxygen-4-phenyl) the propane bismaleimides, 4 of 2-, two (3-amino-benzene oxygen) the sulfobenzide bismaleimides of 4'-, Isosorbide-5-Nitrae-bis-(3-aminophenyl isopropylidene) benzene bismaleimides and two (4-aminophenyl) methane bismaleimides.Bismaleimides can use individually or as mixture.
Also likely use such bismaleimides, wherein the maleimide base group such as methylmaleimido or halomalonimide that are substituted of the maleimide base group of 50% or substituted by Na Dike imide, methyl Na Dike imide or different maleimide base group at the most.The part of maleimide base group also can be substituted by the succinimide of succinimide, phthalic imidine or replacement and phthalimide-based group.
Bismaleimides is prepared by maleic anhydride and diamine by many methods known, and manyly can easily obtain from commercial source.
As previously mentioned, this theme some in, one or more ratio of components of composition such as multiviscosisty component can be the multiviscosisty component of non-acrylic.The component of various non-acrylic can be used.Limiting examples comprises polyolefine, polyvinyl aromatic hydrocarbon, urethane, polycarbonate, polyester, polyethers and these combination, and likely in conjunction with one or more other reagent and/or component.The concrete limiting examples of polyethylene aromatics is polystyrene.
Additive
Various additive and initiator are useful in conjunction with the sizing agent of this theme and composition.Sometimes, term " solidifying agent " is used herein.This term refers to the reagent (one or more) of the polymerization promoting or cause polymkeric substance (one or more) in theme composition or stimulates.Therefore, term solidifying agent comprises single reagent, single stimulation, plurality of reagents, multiple stimulation, the combination of reagent, the combination of stimulation and one or more reagent and one or more combinations stimulated.Generally speaking, solidifying agent (one or more) can be activated, and namely can be activated by radiation, heat, moisture, pressure, at least one that is ultrasonic, that be exposed to chemical reagent and its combination.Usually, as used herein term solidifying agent refers to catalyzer and/or photoinitiator.But will be appreciated that, this term can comprise other reagent various (and stimulation).
Thermocatalyst.Catalyzer can be outside or inside herein.Catalyzer can use with the amount of 0-10wt%, 0.1-10wt%, 0-5wt%, 0.1-5wt%, 0-4wt%, 0.1-4wt%, 0-2wt%, 0.1-2wt% or 0.01-2wt%.The catalyzer be applicable to comprises end-sealed type strong acid catalyst, it is based on by the following acid formed, such as trifluoromethanesulfonic acid (triflicacid), dinonylnaphthalene sulfonic acid (DSA), dinonylnaphthalene disulfonic acid (DDSA), phosphofluoric acid and lithium ammonium antimony (Lewis acid), and can obtain from KingIndustries, such as cXC1615 (diethylamine salt of trifluoromethanesulfonic acid), 155 (the end-sealed type acid catalysts based on DNNDSA), cXC1612 (lithium ammonium antimony), super-A218 (zinc salt of trifluoromethanesulfonic acid), cXC1738 (ammonium hexafluorophosphate) and cXC1614 (trifluoromethanesulfacid acid ammonium).
Alkaline catalysts can be primary amine, secondary amine or tertiary amine.The primary diamines be applicable to is diaminodiphenylsulfone(DDS).Other alkali comprise imidazoles and ketoimine.The imidazoles be applicable to comprises glyoxal ethyline, 2-ethyl 4-methylimidazole, 2-phenylimidazole.In the list of U.S. Patent Application Publication No. 200,9/0,194,320 section of visible imidazole curing agent.Possible alkaline curing agent is Dyhard RU 100 [DICY].
Photoinitiator.Photoinitiator comprises the quick initiator of radical photoinitiator and UV free radical photoinitiator.Photoinitiator can be present in the composition of this theme with the amount of 0-10wt%, 0.01-10wt%, 2-5wt% or 1-3wt%.
Free radical photoinitiator.The azo-compound that thermal initiator comprises peroxide-2 ethyl hexanoic acid tert-butyl ester, tert-Butyl peroxypivalate, peroxide-2 ethyl hexanoic acid tert-pentyl ester, benzoyl peroxide, peroxide acid tert-amyl acetate, peroxide acetic acid butyl ester and sells with trade name Vazo such as such as Vazo52, Vazo67 and Vazo88.
UV free radical photoinitiator.The photoinitiator being suitable for this theme comprises both I type and II type photoinitiator.
I type photoinitiator is restricted to once irradiate experience unit molecule bond cleavage reaction substantially, thus the base that gains freedom.The I type photoinitiator be applicable to is selected from benzoin ether, benzil ketals, α-dialkoxy-methyl phenyl ketone, Alpha-hydroxy alkyl phenyl ketone and acyl-phosphine oxides.The I type photoinitiator be applicable to is commercial available, such as, obtain from LambertiSpa, Gallarate, Italy, EsacureKIP100, or to obtain from the Irgacure651 of Ciba-Geigy, Lautertal, Germany.
Generally speaking, the I type photoinitiator compound be applicable to herein is selected from benzoin ether, benzil ketals, α-dialkoxy-methyl phenyl ketone, Alpha-hydroxy alkyl phenyl ketone and acyl-phosphine oxides.
II type photoinitiator is restricted to and substantially experiences dimolecular reaction, wherein photoinitiator under excited state with serve as the second Compound Phase mutual effect of aided initiating to produce free radical.The II type photoinitiator be applicable to is selected from benzophenone, thioxanthone and two luxuriant titaniums.The aided initiating be applicable to preferably is selected from amine functional monomer, oligopolymer or polymkeric substance, and amino functional monomers and oligopolymer are used in some embodiment thus.Can use primary amine, secondary amine and tertiary amine, tertiary amine is used in some embodiment thus.The II type photoinitiator be applicable to is commercial available, such as, obtain the EsacureTZT from LambertiSpa, Gallarate, Italy, or obtains 2-or the 3-methyl benzophenone from AldrichCo., Milwaukee, Wisconsin, USA.The amine aided initiating be applicable to is commercial available, such as, obtain from RahnAG, Zurich, Switzerland 5275.
The specific examples of II type photoinitiator compound comprises benzophenone and thioxanthone.In a particular embodiment, aided initiating compound such as amine can exist and can interact with II type photoinitiator compound.
Linking agent.Useful linking agent comprises the linking agent of radiation activatable herein, and it is selected from aldehydes, ketone, quinones, thioxanthone and s-triazine.Metal chelate crosslinMng agent catalyzer is also expection.Linking agent can be present in the composition of this theme with the amount of 2 to 95wt%, 0-4wt%, 0.01-4wt%, 0.01-2wt%, 0-2wt%, 0.01-1wt%, 0-1wt%, 0.01-0.5wt% or 0-0.5wt%.
Photosensitizers.Often kind of sensitizer tends to the characteristic response in visible light and ultraviolet spectrum with itself, and they can combinationally use the light expanding response like this, and/or increases the response speed being exposed to light.
Photosensitizers can be used for the composition of this theme with the amount of such as 0-15wt%, 0.01-15wt%, 0-10wt%, 0.01-10wt%, 0-5wt%, 0.01-5wt%, 0-2wt%, 0.01-2wt%, 0-1wt% and 0.01-1wt%.Photosensitizers can be sensitizing dye.
Schematic sensitizing dye is those in following classification: the aminostyryl based compound that ditan, xanthene, acridine, methyne and polymethine, thiazole, thiazine, azine, keto-amine, porphyrin, colored aromatic polycyclic hydrocarbons, thioxanthones, p-replace and aminotriaryl methanes.
Stablizer and processing aid.The stablizer of some classifications and processing aid be expection, comprise oil/wax, antioxidant, photosensitizers, rheology modifier, filler, radical structure component, open loop structure component, epoxy resin, trimethylene oxide, acid anhydride, lactan, lactone, azoles quinoline, isocyanic ester, bismaleimides and azo dioxide (azodioxide).Stablizer and processing aid are used in the composition of this theme with the amount of such as 0-10wt%, 0.1-10wt%, 0-4wt%, 0.1-4wt%, 0-3wt% and 0.1-3wt%.In some embodiments, azo dioxide is used to be useful as stablizer.Such a example commercially obtains the stablizer being called UVTS-52 from the name of HampfordResearch, Inc.ofStratford, CT.UVTS-52 is the azo dioxide of thermal reversion.UVTS-52 (CAS34122-40-2) is considered to Isosorbide-5-Nitrae, 4-trimethylammonium-2,3-diazabicyclo-[3.2.2]-ninth of the ten Heavenly Stems-2-alkene-2,3-dioxide.
Softening agent-oil and wax.The softening agent be applicable to comprises plasticizing oil, such as mineral oil, but also has olefin oligomer and low-molecular weight polymer or glycol benzoate, and the derivative of vegetables oil and animal oil and this kind of oil.The spendable oil derived from oil is the relative high boiling point material temperature of the aromatic hydrocarbon comprising only small proportion.In this, aromatic hydrocarbon should be and is less than 30% by the weighing scale of oil in some embodiments, and is less than 15% more specifically.Alternatively, oil can be fully non-aromatic.The oligopolymer be applicable to comprised as softening agent can be polypropylene, polybutene, hydrogenated polyisoprene, hydrogenated butadiene or analogue, and it has about 100 and molecular-weight average about between 10,000g/mol.The vegetables oil be applicable to and animal oil comprise the glycerine ester class of common fats acid (such as, stearic acid, oleic acid, linolenic acid, linolenic acid) and its polymerization product.Can use other softening agent, condition is that they have applicable consistency.Also the naphthenic mineral oil manufactured by NynasCorporation is had been found that 222B is applicable softening agent.As recognized, softening agent will be normally used for the viscosity reducing overall Adhesive composition, and substantially not reduce the use temperature of sizing agent intensity and/or sizing agent.The selection of softening agent is useful in the formula of specific end-use (such as wet tenacity core application).Because relate to the economic factors of production and material cost, the cost due to softening agent is usually less than the other materials of such as polymkeric substance and tackifying resin in formula, and therefore in order to cost consideration, in sizing agent, the amount of softening agent should maximize.
Wax also can by weight 0% to 20% or the amount of 0.1-20wt% or 0.1-15wt% be used for Adhesive composition, and for reducing the melt viscosity of sizing agent, and insignificantly reduce its sizing agent bonding feature.These waxes also for reducing the open assembly time of composition, and do not affect temperature performance.
The example of useful wax material comprises following.
Lower molecular weight (100-6000g/mol) polyethylene of the hardness value from about 0.1 to the 120 and ASTM softening temperature from about 66 DEG C to 120 DEG C had as measured by ASTM method D-1321 may be used.
May use petroleum wax, such as have from the paraffin of the fusing point of about 130 °F to 170 °F and the Microcrystalline Wax that has from the fusing point of about 135 °F to 200 °F, the latter's fusing point is measured by ASTM method D127-60.
The Atactic Polypropelene had from the ring and ball softening point of about 120 ° to 160 DEG C may be used.
The propylene type wax being called the metallocene catalysis of " Licocene " by the business-like name of ClariantInternational, Ltd., Muttenz, Switzerland may be used.
The wax of metallocene catalysis or the wax of single site catalysed may be used, such as such as at United States Patent (USP) 4,914,253 and 6,319,979 and WO97/33921 and WO98/03603 in describe those.
Paraffin may be used, Microcrystalline Wax, polyethylene wax, Poly Propylene Wax, by product polyethylene wax, the synthetic wax such as fischer-tropsch (Fischer-Tropsch) wax, oxidized Fischer-Tropsch wax, functionalized waxes and its mixture that are manufactured by polymerization carbon monoxide and hydrogen.
Polyolefin-wax.As used herein, term " polyolefin-wax " refers to those polymkeric substance of being made up of olefin monomer unit or long-chain entity.These materials are commercially available with trade name " Epolene " from WestlakeChemicalCo..
There is for the material in some embodiment of this theme the ring and ball softening point of 200 °F to 350 °F.As should be appreciated that, each in these waxes is at room temperature solid.Other useful materials comprise hydrogenated animal, fish and vegetation fat and oil, such as hydrogenated tallow, lard, soya-bean oil, Oleum Gossypii semen, Viscotrol C, menhaden fish oil, Oils,glyceridic,cod-liver etc., and because they are hydrogenated, so they are solids at ambient temperature, find that it is useful about being used as wax material equivalent.These hydride material are called as " animal or plant wax " usually in sizing agent industry.
Antioxidant.Sizing agent also generally includes stablizer or the antioxidant of about 0.1% to about 5%.Stablizer useful in the Adhesive composition of this theme is merged in help to protect above-mentioned polymkeric substance; and thus protect whole sizing agent system not to be heated and the impact of oxidative degradation, heat and oxidative degradation occur in the manufacture of sizing agent and being normally exposed in atmospheric environment during applying and at end product usually.This degraded is proved to be by the deterioration of the outward appearance of sizing agent, physical property and performance characteristic usually.In some embodiments, the antioxidant be particularly useful is the Irganox1010 manufactured by Ciba-Geigya---four (methylene radical (3,5-, bis--tert-butyl-4-hydroxy hydrocinnamate)) methane.High molecular weight hindered phenols and multifunctional phenols in applicable stablizer, the phenols of such as sulfur-bearing and phosphorus.Hindered phenol is known those skilled in the art, and can be characterized as being the phenolic compound also comprising steric bulk group (stericallybulkyradicals) at its phenolic hydroxyl group of next-door neighbour.Especially, tertiary butyl groups at least one ortho position place generally relative to phenolic hydroxyl group on phenyl ring is substituted.Be used for stoping its stretching frequency in the existence of these steric bulk substituted radicals of hydroxyl adjacent place, and correspondingly stop it reactive.This steric hindrance is therefore for phenolic compound provides its stabilising characteristic.Representative hindered phenol comprises:
1,3,5-trimethylammonium-2,4,6-tri-(3-5-bis--tert-butyl-4-hydroxyphenyl) benzene;
Four-3 (3,5-, bis--tert-butyl-4-hydroxyphenyl) propionate;
Octadecane base-3 (3,5-bis-tert-butyl-4-hydroxyphenyl) propionic ester;
4,4'-methylene-bis (4-methyl-6-tert-butylphenol);
4,4'-thiobis (6-tert-butyl-ortho-cresol);
2,6-, bis--tert-butyl phenol;
Two (just pungent sulfenyl)-l, 3, the 5-triazine of 6-(4-hydroxyphenoxy)-2,4-;
2,4,6-tri-(4-hydroxyl-3,5-bis--tert-butyl-phenoxy group)-l, 3,5-triazine;
Two-Octadecane base-3,5-, bis--tertiary butyl-4-hydroxyphenyl phosphoric acid ester;
2-(just pungent sulfenyl) ethyl-3,5-bis--tertiary butyl-4-hydroxy benzoate; With
Six-(3,3,5-, bis--tertiary butyl-4-hydroxy-phenyl) propionic acid sorbitol esters.
By being combined with following, the performance of these stablizers can be further improved; (1) synergistic agent, such as such as Tyox B and phosphorous acid ester; (2) sequestrant and metal passivator, such as such as, ethylenediamine tetraacetic acid (EDTA), its salt and two salicylyl third diimines (disalicylalpropylenediimine).
Ultraviolet inhibitor.Antioxidant can be used for stoping the oxidative attack to Adhesive composition, and it can cause the loss of the gluing intensity of Adhesive composition and interior sticky intensity.Useful antioxidant includes but not limited to amine, such as can be used as N-N'-bis--betanaphthyl-1 that AGERITED obtains, 4-phenylenediamine, phenolic compound, such as from MonsantoChemicalCo. can be used as SANTOVARA obtain 2, 5-bis--(tertiary amyl) Resorcinol, from the four [3-(3' that can be used as IRGANOX1010 acquisition of Ciba-GeigyCorp., 5'-bis--tertiary butyl-4'-hydroxyphenyl) propionic acid ethyl] methane, with the 2-2'-methylene-bis (4-methyl-6-tert-butylphenol) that can be used as ANTIOXIDANT2246 acquisition, and dithiocarbamate, such as dithio butyl carbaminate.
Rheology modifier.Rheology modifier can be added to change the thixotropic behavior of composition.The rheology modifier be applicable to comprises polyamide wax, pyrogenic silica, flow control additive, reactive diluent, anti-settling agent, alpha-olefin, hydroxy-terminated siloxanes-organic copolymer, includes but not limited to hydroxy-end capped polyoxytrimethylene-dimethylsiloxane copolymer and its combination.
Filler.Filler can be used for giving intensity or reducing total cost.Herein useful filler comprise three aluminium hydroxides, calcium hydroxide, with trade name the glass sphere of the expandable microballoon sold, carbon black, titanium dioxide or nickel coating.
In some form of this theme, filler, rheology modifier and/or pigment are present in sizing agent.These can perform some functions, such as change the rheological of sizing agent in the mode expected, from sizing agent or the substrate absorbing moisture or the oil that apply it, and/or promote cohesive failure, instead of bond damage.Other examples of this material comprise calcium carbonate, calcium oxide, talcum, coal tar, textile fiber, glass particle or fiber, aramid fiber slurry, boron fibre, carbon fiber, silicate minerals, mica, flint, wilkinite, wollastonite, kaolin, pyrogenic silica, aerosil or metal-powder such as aluminium powder form or iron powder.In these, calcium carbonate, talcum, calcium oxide, pyrogenic silica and wollastonite are particularly useful, and it combines individually or with some, because these promote the cohesive failure pattern of expectation usually.
Except various concrete composition as herein described, this theme also provides the particular composition of some following explainations in addition.Will be appreciated that these are representativeness, the limiting examples of other concrete compositions of this theme.
The other embodiment of this theme comprises the pressure-sensitive adhesive agent of suitably solidification, it comprises: (a) 50-80wt% has 250,000-750, the vinylformic acid base polymer of the Mw of 000, one or more structure thinners of (b) 20-40wt%, optional vinylformic acid-epoxy functionalized the component of (c) 0-30wt%, the metal chelate crosslinMng agent of (d) 0-0.5wt%, and one or more external catalysts of (e) 0-2wt%.
The another kind of embodiment of this theme is the curable pressure-sensitive adhesive agent formed by blend, wherein said blend comprises the random copolymers of (a) high molecular (such as 400-600kg/mol), and it comprises (i) alkyl acrylate base monomer; (ii) vinyl-acetic ester; (iii) methyl acrylate; (iv) vinylformic acid; (v) crosslinked with silicane monomer; The random copolymers of (b) lower molecular weight (such as 20-50kg/mol), it comprises (i) straight acrylic alkyl ester base monomer, (ii) side chain alkyl acrylate base monomer and (iii) epoxy functionalized methacrylate monomer; C () oligopolymer is such as from the STPE-30 of Wacker; Acrylate-the glycidyl esters of (d) 10-carbon carboxylic acid; (e) cationoid reaction thinner, such as trimethylolpropane oxetane (TMPO); (f) high molecular weight acids functional acrylic diluent monomer, (example is 2-acryloxypropyl phthalic ester); (g) bisphenol-A-type epoxy resin, it is at room temperature semi-solid; (h) linking agent and silane catalyst such as aluminium acetylacetonate.
This theme also provides and uses liquid as herein described and the Method and Technology of composition for combining.Fig. 2 schematically depict the adhesive method 300 according to this theme.In method 300, the layer of composition as described herein or coating 310 are applied to interested substrate or film 320.Composition such as can apply in the spraying of operation 330 place general description or coating by various technology.Then composition that is that be coated with or that otherwise apply presents viscosity by being exposed to such as UV radiation, as in Fig. 2 as shown in 340.In this state, composition is commonly called " A-stage ", and can represent the T-peel value of 0.17lbs and 180 ° of strippings of 0.64lbs in some embodiments.Then another material layer such as copper as shown in 350 contact with viscosity A-phase composition 310 with the laminate of aluminium foil.The laminated assembly of gained relates to one or more processing station such as laser pattern and forms station 360, and it is formed as the 370 figuratum laminates described in Fig. 2.Depend on end-use requirement, the removal of other processing such as foil clout (matrix) can be carried out, such as collect useless clout 380 at operation 375 place.The laminate of the processing of gained is shown as 385.Then the laminate 385 processed can experience one or more other process operations, is such as shown as the thermofixation of 390.After thermofixation, composition 310 is called as " B-stage ", its usually represent with its A-stage those compared with significantly larger T-peel off and 180 ° of peel value.Such as, the T-peel value in B-stage can be about 0.37lbs and 180 ° peel value can be about 3.6lbs.Solidifying product can be collected with roll form or sheet form 395.
Generally speaking, in the various embodiments of this theme, when by any reagent as described herein or stimulate at least in part curing composition time, liquid as herein described or composition can present viscosity or represent usually the characteristic relevant to pressure-sensitive adhesive agent.In some form, realize the first solidification or partially cured by composition being exposed to UV radiation, electron beam, heat or these combination.In addition, by being exposed to heat, comprise the chemical reagent of water or moisture, pressure or its combination, then this partially cured composition can be solidified further.
This theme composition can be used for various application.Such as, the application of concrete purposes can relate to the foam article manufactured by composition as herein described.The pore forming material of one or more routines can be merged in the composition of this theme, carries out bubbling or expanding, thus produces foam layer or article.Composition can also for being adhesively bonded to other surfaces, substrate or object by foam article.
More specifically, this theme can be used for combining or the combination of otherwise coherent film and film, film and paper tinsel, apron and paper tinsel, apron and film, fabric and fabric, fabric and almost any other material or substrate such as film, paper and metal, paper and metal, metal and metal, film and other plastics, plastics and plastics and these and other surperficial, material and/or substrate.This theme can also for providing the chemoresistance to various surface and substrate, such as anticorrosive.Such as, this theme can be used for providing chemical resistance label, and solvent tolerance laminate such as solvent tolerance glass and paper tinsel assembly.This theme also can be used for forming rete laminate, such as film and rete laminate.The application of another expection of this theme is the field of shrinkage sleeve and shrinkage sleeve label.In addition, this theme can be widely used in the solvent welding of two membranes.Still Another Application field relates to component and especially metal tube such as oil and the corrosion protection of gas pipeline.The composition of this theme and method can be used for providing or increase anti-impact force, structural integrity and anticorrosive or be exposed to the protection of environmental factors.Concrete and the limiting examples of this corrosion protection is to provide skin, internal layer or along both the external peripheral surface of pipe and/or inner circumferential surface.That composition can experience bending, flexure or other stress and not cracking according to another remarkable benefit of some composition of this theme.If such as composition (one or more) is applied to pipeline, this expects.The application of still another expection of some composition of this theme forms glass fibre structure such as marine ship body, some sports goods and structure unit.The still Another Application of this theme is " roll tightly, tighten " (ROSO) application.
Embodiment
Embodiment 1-4
The sizing agent of the suitable solidification of some embodiment of this theme can be described to the acrylate copolymer mixed with reactive diluent, oligopolymer and structural constituent.Provide the other details of this theme in the following embodiments.
Embodiment 1: the high-performance PS A with moisture cured oligopolymer (sizing agent of suitably solidification)
Embodiment 1 is the acrylate copolymer of the oligopolymer (STPE-30) with potential reaction.STPE-30 oligopolymer is by silane-silane condensation reaction solidification.Optionally, base polymer also can have silane functionality and can with reactive oligomers coreaction.
Embodiment 2: the high-performance PS A with the oligopolymer (sizing agent of suitably solidification) of UV-curable
Embodiment 2 is the acrylate copolymer mixed with reactive diluent and structural constituent, its by UV expose trigger with by sizing agent from liquid conversion for solid PSA, and by being heating and curing to abundant intensity during film and rete pressure.
In order to original position moisture-curable is incorporated to high performance pressure sensitive sizing agent system, acrylate copolymer, tackifier and reactive oligomers are mixed in a solvent.After applying as described herein and being exposed to humidity, under the condition of the reaction causing a part of oligopolymer potential, the applied form that becomes band of this system.
Embodiment 3: the high-performance PS A with moisture cured oligopolymer (sizing agent of suitably solidification, solid ingredient)
The composition of embodiment 3 is the high-performance PS A with moisture cured oligopolymer (sizing agent of suitably solidification).In order to original position moisture-curable is incorporated to high performance pressure sensitive sizing agent system, acrylate copolymer, tackifier and reactive oligomers is mixed in a solvent or otherwise combines.In application with after being exposed to humidity, under the condition of the reaction causing a part of oligopolymer potential, the applied form that becomes band of this system.
The composition of table 3: embodiment 3PSA
Weight percentage Component
54.45％ DEV-8631 U (vinylformic acid base polymer)
25％ Terpene phenols tackifier (softening temperature 110-120 DEG C)
20％ Terpene phenols tackifier (softening temperature 110-120 DEG C)
0.55％ Metallo-chelate Acetyl Acetone aluminium (linking agent & catalyzer)
Vinylformic acid base polymer is high molecular (400-600kg/mol) random copolymers, and it comprises (a) alkyl acrylate base monomer; (b) vinyl-acetic ester; (c) methyl acrylate; (d) vinylformic acid; (e) crosslinked with silicane monomer.
The example of vinylformic acid base polymer is DEV8631U, and its random copolymers of molecular weight (Mw) for having about 518,000g/mol, it comprises following compositions.
Table 4: the vinylformic acid base polymer (i.e. DEV8631U) in embodiment 3PSA
Component Weight percentage
2-EHA (base monomer) 57.95
Vinyl-acetic ester (modified monomer) 25
Methyl acrylate 15
Vinylformic acid (high Tg monomer, crosslink sites) 3
Methacryloxypropyl trimethoxy silane (cross-linking monomer) 0.05
Reactive oligomers is silane-terminated polyether (oligopolymer), is such as shown as the STPE-30 from Wacker of formula (22) as follows.STPE-30 is silane-terminated polyether.Two Silante terminated polypropylene glycols of display are based on identical polyethers.Its difference is end group.
Linking agent and catalyzer are aluminium acetylacetonate and are shown as formula (23) as follows:
Describe adhesive method in figure 6.With reference to figure 6, generally speaking, as follows according to the combining method 200 of this theme.In operation 210, composition as described herein is applied or be otherwise applied on film or substrate.The example of this film is release film.Be applicable to applying after, drying composition, this also comprises the removal of any solvent at least partially in composition usually, as operate 220 describe.Dry representative of conditions comprises and is exposed to 80 DEG C and continues about 5 minutes.In operation 230, then composition is by being exposed to heat and/or humidity is properly cured, thus forms high strength sizing agent 240.The condensation reaction occurred shows below:
～Si-OCH 3+H 2O→～Si-O-Si～+CH 3OH
Fig. 1 depicts the dynamic mechanical analysis of the pressure-sensitive adhesive agent of the suitable solidification of embodiment 3.
Embodiment 4: curablely carry out the liquid composition (suitable solidify sizing agent) of B-stage for PSA (UV) during film and rete pressure
In example 4, acrylate copolymer and reactive addition thinner and structure mixing diluents.
Table 5: the composition of embodiment 4 liquid composition
Weight percentage Component
15％ ACE monomer stage component (reactive diluent)
10％ V2100 (reactive diluent)
10％ Epon 834 (structural constituent)
9％ TMPO trimethylene oxide (structural constituent)
56％ EB14-04 (acrylate copolymer)
The example of reactive diluent is ACE monomer A CE tMvinylformic acid hydroxyl ester monomer, is provided by MomentivePerformanceMaterials, LeverkusenGermany, and it is vinylformic acid and Cardura tMreaction product.Cardura is Versatic tMthe glycidyl esters of Acid10, it is the highly branched saturated carboxylic acid comprising 10 carbon atoms.ACE has the unique texture in conjunction with large volume hydrophobic tail, pendant hydroxyl groups and acrylate-functional groups, and molecular weight is about 300.ACE has the structure of the formula that is shown as follows (24):
Another kind of reactant thinner---high molecular weight acids functional acrylic diluent monomer V-2100, it is to obtain the 2-acryloxypropyl phthalic ester from New York SanEstersCorporation, is shown as formula (25) as follows:
Structural constituent is EPON tMresin 834, its for can obtain from MomentivePerformanceMaterials at room temperature for semisolid BPA base epoxy.Use the system of EPON resin 834 to be configured to and can be used for various high solid and modified by tar coating, high tough sizing agent, laminating material and preimpregnation formed material.Because its higher molecular weight, EPON resin 834 provides the system response of increase compared with liquid level BPA epoxy resin, surface adhering and cured resin toughness, but is reduction of raised temperature performance.EPON resin 834 is particularly useful in the application needing extra surface adhering, curing speed or toughness.
Another kind of structural constituent is cationoid reaction thinner, such as trimethylolpropane oxetane (TMPO).UV/EB cationic formulation can be formed, and it mainly comprises resin, thinner and photoinitiator, such as 3,4 epoxycyclohexyl-methyl-3,4 epoxy cyclohexane carboxylic acid (being shown as formula (26) as follows) and the TMPO as reactive diluent of Primary resins:
Acrylate component is lower molecular weight (20-50kg/mol) random copolymers, it comprises (a) straight acrylic alkyl ester base monomer, (b) side chain alkyl acrylate base monomer and (c) epoxy functionalized methacrylate monomer.
The example of acrylate component is following low-molecular weight polymer EB14-04, its random copolymers of Mw for having about 40,000g/mol:
Table 6: the example of acrylate component, the EB14-04 namely in embodiment 4 liquid composition
Component Weight percentage
Butyl acrylate (base monomer) 40
Tert-butyl acrylate 40
S-100 (alicyclic epoxy official energy methacrylate monomer) 30
Describe adhesive method in figure 6.
Embodiment 5-7
Embodiment 5-7 illustrates and can be used for being formed the component of this theme and the polymerization process of composition.
Embodiment 5: component is polymerized with the distant pawl of plan, uses SFRP reagent to have the embodiment of epoxy functionalities
Following preparation has the acrylic copolymer of the active functionality being arranged in the section adjacent with polymer chain terminal, is shown as formula (27) as follows:
Be equipped with the Blocbuilder of 1500ml reactor feed 8.30g from ArkemaInc of heating jacket, agitator, reflux exchanger, charging stock tank and nitrogen inlet.Monomer and solvent are added into feed containers with following amounts:
22.30g 2-EHA;
64.30g ethoxy ethoxy ethyl propenoate; With
85.30g propyl acetate
Blocbuilder in reactor and the monomer in feed containers and solvent at room temperature clean 30 minutes with constant nitrogen bubble.After this maintenance, monomer and solvent mixture are fed to reactor to produce the non-reacted section of the small portion adjacent with reactive polymer pattern, to add acrylate group to Blocbuilder.Then reactor feed mixture is heated to and is greater than 70 DEG C (reactor jacket 75 DEG C), and keeps 30min.After second keeps, reactor feed mixture is cooled to room temperature (about 25 DEG C).Once reactor feed reaches room temperature, the SynasiaEpoxyS-100 of 13.40g is fed to reactor.After this epoxy resin of interpolation, reactor is sealed, and at room temperature with other 30 minutes of constant nitrogen bubble cleaning.After 30 minutes bubblings, reactor mixture is heated to 100 DEG C.When reactor mixture is heated to 100 DEG C, the ethoxy ethoxy ethyl propenoate of 579.10g and the 2-ethylhexyl acrylate of 201.10g are fed to feed containers, and clean with constant nitrogen bubble.When reactor mixture reaches 100 DEG C, set of time is zero (T=0).At T=15 minute place, sampling was used for gas chromatographic analysis to check conversion of monomer.When conversion of monomer is identified (about 30 minutes, T=45), under reactor mixture remains on the temperature between 110 DEG C and 117 DEG C under reflux, until the epoxy resin >90% transformed (2-EHA and EOEOEA of about 70% transforms).In this conversion place, the reagent feeds mixture with active nitrogen gas cleaning was added into reactor 180 minutes periods.During reagent feeds, the temperature of reaction remains on 110-118 DEG C under reflux.After reagent feeds completes, maintain reaction conditions until realize the conversion of 2-EHA and EOEOEA of 80%.This is the remainder in order to produce the non-reacted section adjacent with function end segments.In this conversion place, the propyl acetate of SynasiaEpoxyS-100 and 13.40g of 13.40g by quick feeding to reactor (about 2min.) to produce final function end segments.Maintain reaction conditions until realize being greater than the conversion of 2-EHA and EOEOEA of 98%.Then gained solution polymer is cooled to envrionment temperature and discharges from reactor.The total theoretical Mn of polymkeric substance is 41,000g/mol.Each non-reacted centre portion is 32,000g/mol and function end segments is 4,500g/mol.
The molecular weight (Mn) of the total acrylate copolymer measured is 20,043g/mol (gel permeation chromatography by relative to polystyrene standard) and polymolecularity is 3.02.So the Mw calculated is 60,530g/ mole.
Embodiment 6: with being polymerized of individual feature end segments (tadpole), uses SFRP reagent to have the embodiment of alcohol functionalities
Following preparation has the acrylic copolymer of the active functionality being arranged in the section adjacent with polymer chain terminal, is shown as (28):
At the Blocbuilder of the 1500ml reactor feed 11.41g of outfit heating jacket, agitator, reflux exchanger, charging stock tank and nitrogen inlet.Monomer and solvent are added into feed containers with following amounts:
The n-butyl acrylate of 105.93g;
26.48g tert-butyl acrylate; With
The vinylformic acid 4-hydroxypropyl acrylate of 17.26g
Blocbuilder in reactor and the monomer in feed containers and solvent at room temperature clean 30 minutes with constant nitrogen bubble.After this maintenance, monomer and solvent mixture are fed to reactor to produce the reactive section of the small portion adjacent with reactive polymer pattern, to add acrylate group to Blocbuilder.Then reactor feed mixture is heated to and is greater than 70 DEG C (reactor jacket 75 DEG C), and keeps 30min.After second keeps, reactor mixture is heated to 100 DEG C.When reactor mixture is heated to 100 DEG C, the butyl acrylate of 1071.14g and the tert. butylacrylate of 267.78g are fed to feed containers, and clean with constant nitrogen bubble.When reactor mixture reaches 100 DEG C, timing register is set to zero (T=0), and remains between 100 and 105 DEG C.At T=15 minute place, sampling was used for gas chromatographic analysis to check conversion of monomer.When conversion of monomer is identified (about 30 minutes, T=45), under reactor mixture remains on the temperature of 100 DEG C and 105 DEG C, until the butyl acrylate >80% transformed.In this conversion place, the reagent feeds mixture with active nitrogen gas cleaning was added into reactor within 180 minutes periods.During reagent feeds, the temperature of reaction remains between 100-105 DEG C.After completing reagent feeds, maintain reaction conditions until realize being greater than the conversion of the butyl acrylate of 98%.Then resulting polymers is cooled to envrionment temperature and is discharged from reactor.The total theoretical Mn of polymkeric substance is 50,000g/mol.Each non-reacted section is 45,000g/mol and function end segments is 5,000g/mol.
The molecular weight (Mn) of the total acrylate copolymer measured is 53,591g/mol (gel permeation chromatography by relative to polystyrene standard) and polymolecularity is 1.51.So the Mw calculated is 80,922.
Embodiment 7: the random sense distributed embodiments with alcohol functionalities
Following preparation has the acrylic copolymer of the active functionality being positioned at whole polymer chain at random, is usually shown as follows (29):
At the toluene of the 1500ml reactor feed 139.37g of outfit heating jacket, agitator, reflux exchanger, charging stock tank and nitrogen inlet.Monomer is added into feed containers with following amounts:
83.16g 2-EHA;
239.51g ethoxy ethoxy ethyl propenoate; With
The vinylformic acid 4-hydroxypropyl acrylate of 9.98g
Solvent and initiator are added into the second feed containers with following amounts:
3.33g lauroyl peroxide; With
30.00g toluene
Toluene in reactor, the initiator mixture in feed containers and monomer at room temperature clean 30 minutes with constant nitrogen bubble.After this maintenance, the toluene in reactor is heated to 105 DEG C, wherein has a small amount of backflow to leave condenser.At this point, monomer and initiator mixture were fed to reactor in 90 minutes.During reagent and initiator feed, under reactor mixture remains on the temperature between 105 DEG C and 116 DEG C under reflux.After reagent and initiator feed complete, maintain reaction conditions 60 minutes.During 60 minutes keep, in feed containers, prepare detonation (cook-off) catalyst charge.Detonation catalyst charge is made up of the toluene of 24.28g and the special pentyl ester of the peroxidation PIVALIC ACID CRUDE (25) of 0.37g.Detonation catalyzer bubbling 15 minutes under constant nitrogen purge.After 60 minutes keep, detonation catalyzer was fed to reactor in 30 minutes.Once detonation catalyst charge is depleted, maintains reaction >110 DEG C and continue 60 minutes.Then the solution polymer of gained is cooled to envrionment temperature and discharges from reactor.
The molecular weight (Mn) of the total acrylate copolymer measured is 13,301g/mol (gel permeation chromatography by relative to polystyrene standard) and polymolecularity is 2.76.So the Mw calculated is 36,711.
Embodiment 8-39
Embodiment 8-33 based on the acrylate copolymer mixed with reactive diluent and structural constituent, its by UV expose trigger with by sizing agent from liquid conversion for solid PSA, and by being heating and curing to abundant intensity (structure).
Illustrate embodiment 8-33 in table 7.
Table 7: the embodiment 8-33 of Adhesive composition
In table 7, IR refers to anti-impact force, measures according to ASTM-G14-04 (2010).Rolling Ball Tack measures according to ASTM-D3121-06.
Embodiment 34-36 illustrates lap shear and the Rolling Ball Tack measurement of the other Adhesive composition of this theme.
Embodiment 34 is the acrylate copolymer mixed with structural constituent, and is PSA through mild heat drying, and is then triggered the structure combination of solidifying producing between two substrates completely by higher heat.
Embodiment 35 is the acrylate copolymer mixed with both reactive oligomers and structural constituent, and is PSA through mild heat drying, and is then triggered the structure combination of solidifying producing between two substrates completely by higher heat.
Embodiment 36 is the acrylate copolymer mixed with reactive diluent and structural constituent, its by low beat exposure trigger with by sizing agent from liquid conversion for PSA, and by higher thermofixation to abundant intensity (structural).
Embodiment 34:AS-2549 vinylformic acid PSA and AAA is cross-linked, and mixes with SynasiaS-21 epoxy resin, and at 90 DEG C leniently dry 10min with solvent-free PSA film of casting.Initiator for the thermofixation of epoxy resin is being less than sluggish temperature 95 DEG C mostly.At desciccator diaphragm with after producing PSA adhesive tape, this adhesive tape can be applied to expecting given substrate to be bonded.Upon application of this adhesive tape, apply other heat and be converted into abundant intensity to cause sizing agent.Structure is formed at being combined in 140 DEG C, continues 15 minutes.The description display of the lap shear test of embodiment 34 in figure 3.This program is as follows:
The lap shear data (Al and Al) of embodiment 34 present in table 8.
Table 8: lap shear data
Following mensuration lap shear.ASTMD-1002 standard method of test, it connects the apparent shearing resistance (metal and metal) (reference) of viscosity in conjunction with metal sample for the single overlap joint by tensile loading.Sizing agent thickness is 0.0024 inch of +/-0.0006 inch.Load is 1 inch per minute clock.Measure peak load.
Embodiment 35:AS-2549 vinylformic acid PSA and AAA is cross-linked, and mixes with SynasiaS-21 epoxy resin and KH4-67, and at 90 DEG C leniently dry 10min with solvent-free PSA film of casting.Sluggish for the initiator of the thermofixation of epoxy resin mostly in the temperature being less than 95 DEG C.At desciccator diaphragm with after producing PSA adhesive tape, this adhesive tape can be applied to expecting substrate to be bonded.Upon application of this adhesive tape, apply other heat to cause sizing agent to be converted into abundant intensity.Structure is formed at being combined in 140 DEG C, continues 15 minutes.Fig. 4 depicts the program of lap shear test in embodiment 35.
The lap shear data (Al and Al) of embodiment 35 are presented in table 9.
Table 9: lap shear data
Embodiment 36:KH4-105 acrylic acid oligomer mixes with EPON828 epoxy resin, TMPO and SiloquestA-187.It leniently solidifies 7min with PSA film of casting at 110 DEG C.Initiator for the thermofixation of epoxy resin to be less than at the temperature of 110 DEG C slowly.At desciccator diaphragm with after producing PSA adhesive tape, this adhesive tape can be applied to expecting substrate to be bonded.Upon application of this adhesive tape, apply other heat and be converted into abundant intensity to cause sizing agent.Structure is formed at being combined in 140 DEG C, continues 15 minutes.
The lap shear data (Al and Al) of embodiment 36 present in table 10.
Table 10: the Rolling Ball Tack data of embodiment 36
Embodiment 37: be applied to substrate according to the liquid of this theme and suitably solidify by being exposed to actinic radiation subsequently.Describe diagram in Figure 5.Specifically, Fig. 5 schematically depict and applies liquid or other compositions on film, label and/or container, and is exposed to actinic radiation, thus suitably solidified liquid or composition.Provide there is liquid or composition 20 as described herein and be coated with region, face or the film on surface or the source of label 10.In some embodiments, one or more regions 25 of the sizing agent sticked together or band 30 can be provided to help primitively to fix film or label extremely interested container 40.Before, during and/or after the applying film be applicable to or label to container, actinic radiation 50 is caused coating, thus adhere to and/or solidified coating, and produce the container 45 of mark.This is expressed as operation A usually in Figure 5.After initial applying film or label, removing and/or the applying of heat can be carried out.Other operation can be carried out before, during and/or after operation (one or more) A.Fig. 5 also diagrammatically illustrates wherein multiple container 140 and receives the successive processes 100 of film or label, and it is exposed to actinic radiation thus produces the container 145 of multiple mark in closure member 150.
Following table 11 comprises the exemplary formulation of the embodiment representing this theme.(namely said preparation comprises the multiviscosisty component of following explaination, free radical addition thinner, structure thinner and photoinitiator and additive 1010).
Table 11: the illustrative embodiments of Adhesive composition
Following table 12 shows the performance data of the selection of some preparation in table 11.
Table 12: the performance data of the selection of preparation in table 11
Embodiment 38: illustrate in following table 13 and 14 according to two kinds of this theme other Adhesive composition.
Table 13: Adhesive composition EXP-MW2-070-A
Table 14: Adhesive composition EXP-MW2-070-B
Embodiment 39: illustrate the some other composition according to this theme in following table 15 and 16.The embody rule of these compositions is " roll tightly, tighten " (ROSO) mark or correlation technique.
Table 15: roll tightly, tighten composition
Table 16: roll tightly, tighten composition
From the application and development in future of this technology, other benefits many will become apparent undoubtedly.
The all patents mentioned herein, the application of publication and article are merged in their entirety herein by reference.
This theme comprises the component of various composition as herein described and the combination of aspect.Therefore, such as, this theme comprises one or more components of a kind of embodiment and/or one or more other components and/or integrate features of feature and other embodiments (one or more).
As described above herein, this theme solves and strategy before, system and/or device-dependent many problems.But; will be appreciated that; those skilled in the art to describing herein and explain to explain that the layout of the details of this theme essence, material and component carries out various change, and can not deviate from principle and the scope of claimed theme, expressed by claims.

Claims (8)

1. a pressure-sensitive adhesive agent for suitably solidification, it comprises:
20-80wt% has 100,000 to 1, the vinylformic acid base polymer of the Mw of 000,000;
The tackifier of 0-30wt%;
At least one liquid reactions component of 5-40wt%;
At least one vinylformic acid-epoxy functionalized the component of 0-30wt%;
The epoxy functionalized alkene of 0-30wt%; With
Metal chelate crosslinMng agent-the catalyzer of 0-2wt% and at least one of external catalyst.
2. sizing agent according to claim 1, wherein said vinylformic acid base polymer has 250,000 to 750, the Mw of 000.
3. a pressure-sensitive adhesive agent for suitably solidification, it comprises:
50-80wt% has 250,000 to 750, the vinylformic acid base polymer of the Mw of 000;
At least one structure thinner of 10-30wt%;
At least one metal chelate crosslinMng agent of 0-0.5wt%;
The solidifying agent of 0-2wt%; With
Stablizer/the processing aid of 0-10wt%.
4. a pressure-sensitive adhesive agent for suitably solidification, it comprises:
50-80wt% has 250,000-750, the vinylformic acid base polymer of the Mw of 000;
At least one structure thinner of 20-40wt%;
At least one vinylformic acid-epoxy functionalized the component of 0-30wt%;
At least one metal chelate crosslinMng agent of 0-0.5wt%;
The solidifying agent of 0-2wt%; With
Stablizer/the processing aid of 0-10wt%.
5. a liquid for suitably solidification, it comprises:
The multiviscosisty component of 70-80wt%, it comprises and has 15,000-250, the acrylic copolymer of the Mw of 000;
At least one structure thinner of 15-20wt%;
The photoinitiator of 0.01-5wt%; With
Stablizer/the processing aid of 0-10wt%.
6. the liquid of suitable solidification according to claim 5, wherein said acrylic copolymer has 18,000 to 70, the Mw of 000.
7. a pressure-sensitive adhesive agent for suitably solidification, it comprises:
50-80wt% has 250,000 to 750, the vinylformic acid base polymer of the Mw of 000;
At least one structure thinner of 10-30wt%;
At least one metal chelate crosslinMng agent of 0-0.5wt%;
The solidifying agent of 0-2wt%; With
Stablizer/the processing aid of 0.1-10wt%.
8. sizing agent according to claim 7, wherein said solidifying agent is catalyzer, and described stablizer/processing aid is Isosorbide-5-Nitrae, 4-trimethylammonium-2,3-diazabicyclo-[3.2.2]-ninth of the ten Heavenly Stems-2-alkene-2,3-dioxide.
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CN110628351A (en) * 2018-06-25 2019-12-31 上海海优威新材料股份有限公司 Protective film for protecting a workpiece in a processing state and use thereof

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