CN105051134B - Adhesive and correlation technique - Google Patents

Abstract

Describe a kind of appropriate cured pressure-sensitive adhesive agent composition comprising one or more thickening components, structure diluent, free radical diluent and additive, such as crosslinking agent, external catalyst, photoinitiator and stabilizer/processing aid.Thickening component can be acrylic acid or non-acrylic acid.

Description

Adhesive and correlation technique

Cross reference to related applications

This application claims the priority for the U.S.Provisional Serial 61/711,386 for being filed on October 9th, 2012.

Technical field

This theme relates generally to the reactive oligomers blended with acrylate or ethylene-propylene perester radical plinth polymer And/or compound.In certain forms, non-acrylate polymers are used in blend.The blend is generated comprising oligomeric The pressure-sensitive adhesive agent (PSA) of potential degree of functionality on object and/or the additive for being suitably crosslinked.Crosslinking can be urged by surface Change, UV irradiation or other curing mechanisms trigger.

Specifically, this theme is related to pressure-sensitive adhesive agent composition, relate more specifically to have over a wide temperature range The pressure-sensitive adhesive agent of high adhesiveness.The theme further relates to suitably solidify liquid composition.This theme further relate to forming method and Use the method for this composition.The theme is further to the foamed product for being incorporated to the composition.

Summary of the invention

This theme relates generally to through the suitably cured pressure-sensitive adhesive agent of UV light, surface catalysis or some other mechanism, and And it obtains the intensity more much higher than typical PSA.The adhesive usually passes through reactive oligomers and one or more high scores Son amount acrylate polymer blends to be formed.One example is the acrylate copolymer of silane-functional and gathering for silicyl sealing end The blend of ether.The blend is inherent viscosity, and can be by the way that the blend is exposed to the chemical combination comprising oligomeric silane Object is cured, and the oligomeric silane can be such as printed on matching surface.

In one embodiment, the pressure-sensitive adhesive agent of this theme or appropriate cured composition are by including blending below Object is formed: (a) reactive oligomers and (b) high-molecular-weight propylene acid ester polymer.The blend is inherent viscosity, and is led to It crosses and the blend is exposed to the compound comprising oligomeric silane is cured, the oligomeric silane can be by printing on the surface It is introduced into.

The another embodiment of this theme is appropriate cured pressure-sensitive adhesive agent comprising: (a) 20-80 weight percent The thickening component (bodying component) of number (wt%) comprising have 5,000 to 1,000,000, in certain embodiment party It is 15,000-250,000 in formula, and the acrylic acid for the molecular weight (Mw) for being 15,000-100,000 in still other embodiments Base polymer, (b) one or more structure diluents of 5-50wt%, (c) one or more free radicals of 10-80wt% add At diluent, (d) one or more crosslinking agents of 0-4.0wt%, (e) one or more external catalysts of 0-4.0wt%, (f) one or more photoinitiators of 0.01-10wt%, and (g) one or more stabilizer/processing of 0-10.0wt% help Agent.

The yet another embodiment of this theme is appropriate cured pressure-sensitive adhesive agent comprising (a) 20-80wt%'s is thick Change component comprising have 1,000 to 500,000, is in some embodiments 1,000-100,000, and in still other realities It applies for 1000-50 in mode, the base polymer of 000 Mw, it is fragrant that the base polymer is selected from polyolefin, polyvinyl Hydrocarbon, polyurethane, polycarbonate, polyester, polyethers and a combination thereof, (b) one or more structure diluents of 5-50wt%, (c) 10- One or more free radical addition diluents of 80wt%, (d) one or more crosslinking agents of 0-1.0wt%, (e) 0- One or more external catalysts of 4.0wt%, (f) one or more photoinitiators of 0.01-10wt%, and (g) 0- One or more stabilizer/processing aids of 10.0wt%.

The other embodiment of this theme includes appropriate cured pressure-sensitive adhesive agent comprising: (a) 20-80wt% Acrylic acid base polymer with 100,000 to 1,000,000 with the Mw for being in some embodiments 250,000-750,000 Object, (b) one or more tackifier of 0-30wt%, (c) one or more liquid reactions components of 5-40wt%, (d) 0- The epoxy functionalized component of the acrylic acid-of 30wt% and/or epoxy functionalized alkene, and (e) metal chelate crosslinMng agent-of 0-2wt% Catalyst and/or external catalyst.

The other embodiment of this theme includes appropriate cured pressure-sensitive adhesive agent comprising: (a) 50-80wt% Acrylic acid base polymer with 250,000-750,000 Mw, (b) one or more structure diluents of 10-30wt%, (c) metal chelate crosslinMng agent of 0-0.5wt%, (d) one or more external catalysts of 0-2wt%, and (e) 0-10wt% Stabilizer/processing aid.

The other embodiment of this theme includes appropriate cured pressure-sensitive adhesive agent comprising: (a) 50-80wt% Acrylic acid base polymer with 250,000-750,000 Mw, (b) one or more structure diluents of 20-40wt%, (c) the epoxy functionalized component of optional acrylic acid-of 0-30wt%, (d) metal chelate crosslinMng agent of 0-0.5wt%, (e) 0- One or more external catalysts of 2wt%, and (f) stabilizer/processing aid of 0-10wt%.

The other embodiment of this theme includes appropriate cured liquid comprising: (a) the thickening group of 5-70wt% Point comprising have 5,000 to 1,000,000, is in some embodiments 15,000-250,000, and in still other implementations It is the acrylic acid base polymer of 15,000-100,000 Mw in mode, (b) one or more structures dilution of 5-40wt% Agent, (c) one or more free radical addition diluents of 30-95wt%, (d) one or more external catalysts of 0-10.0wt% Agent, (e) one or more photoinitiators of 0-10wt%, (f) one or more photosensitizers of 0-10wt%, and (g) 0- The stabilizer (one or more) of 10wt%.

The other embodiment of this theme includes appropriate cured liquid comprising: (a) the thickening group of 5-50wt% Point comprising the acrylic acid base polymer with 15,000 to 100,000 Mw, (b) one or more knots of 50-95wt% Structure diluent, (c) one or more external catalysts of 0.01-10wt%, and (d) stabilizer/processing aid of 0-10wt%.

The other embodiment of this theme includes appropriate cured liquid comprising the thickening group of (a) 30-70wt% Point comprising the acrylic copolymer with 15,000-100,000 Mw, (b) one or more structures dilution of 7-70wt% Agent, (c) one or more free radical addition diluents of 7-70wt%, (d) one or more photoinitiators of 2-10wt%, (e) one or more antioxidants of 0-1%, and (f) stabilizer/processing aid of 0-10wt%.

The other embodiment of this theme includes appropriate cured liquid comprising: (a) the thickening group of 5-70wt% Point comprising have 5,000 to 1,000,000, is in some embodiments 15,000-250,000, and in still other implementations It is the acrylic acid base polymer of 15,000-100,000 Mw in mode, (b) one or more structures dilution of 5-80wt% Agent, (c) one or more free radical addition diluents of 5-70wt%, (d) one or more external catalysts of 0-5.0wt% Agent, (e) one or more photoinitiators of 0-10wt%, (f) one or more photosensitizers of 0-10wt%, and (g) 0- Stabilizer/processing aid of 10wt%.

The other embodiment of this theme includes appropriate cured liquid comprising: (a) the thickening group of 10-15wt% Point comprising the acrylic acid base polymer with 15,000-100,000 Mw, (b) one or more knots of 45-60wt% Structure diluent, (c) one or more free radical addition diluents of 30-40wt%, (d) 0.01-2.0wt%'s is one or more External catalyst, (e) photoinitiator of 0.01-10wt%, (f) one or more photosensitizers of 0-10wt%, and (g) 0- Stabilizer/processing aid of 10wt%.

The other embodiment of this theme includes appropriate cured liquid comprising: (a) the thickening group of 5-70wt% Point comprising have 1,000 to 500,000, is in some embodiments 1,000-100,000, and in still other embodiment party In formula for 1,000-50,000 Mw non-acrylic acid base polymer, the non-acrylic acid base polymer be selected from polyolefin, Polyvinyl aromatic hydrocarbon, polyurethane, polycarbonate, polyester, polyethers and a combination thereof, (b) one or more structures of 5-80wt% Diluent, (c) one or more free radical addition diluents of 0-40wt%, (d) one or more outsides of 0-5.0wt% are urged Agent, (e) one or more photoinitiators of 0-10wt%, (f) one or more photosensitizers of 0-10wt%, and (g) 0- Stabilizer/processing aid of 10wt%.

The other embodiment of this theme includes appropriate cured liquid comprising: (a) the thickening group of 5-50wt% Point comprising have 5,000 to 1,000,000 and the non-acrylic acid of 15,000-100,000 Mw gathers in some embodiments Conjunction object, (b) one or more structure diluents of 50-95wt%, (c) one or more external catalysts of 0.01-10wt%, (d) stabilizer/processing aid of 0-10wt%.The non-acrylate copolymer is selected from polyolefin, polyvinyl aromatic hydrocarbon, gathers Urethane, polycarbonate, polyester, polyethers and a combination thereof.

The other embodiment of this theme includes appropriate cured liquid comprising: (a) the thickening group of 5-70wt% Point comprising have 1,000 to 500,000, is in some embodiments 1,000-100,000, and in still other embodiment party In formula for 1,000-50,000 Mw non-acrylic acid base polymer, the non-acrylic acid base polymer be selected from polyolefin, Polyvinyl aromatic hydrocarbon, polyurethane, polycarbonate, polyester, polyethers and a combination thereof, (b) one or more structures of 5-80wt% Diluent, (c) one or more free radical addition diluents of 5-70wt%, (d) one or more outsides of 0-5.0wt% are urged Agent, (e) one or more photoinitiators of 0-10wt%, (f) one or more photosensitizers of 0-10wt%, and (g) 0- Stabilizer/processing aid of 10wt%.

The other embodiment of this theme includes appropriate cured liquid comprising: (a) the thickening group of 10-15wt% Point comprising have 1,000 to 500,000, is in some embodiments 1,000-100,000, and in still other embodiment party In formula for 1,000-50,000 Mw non-acrylate copolymer, (b) one or more structure diluents of 45-60wt%, (c) One or more free radical addition diluents of 30-40wt%, (d) one or more external catalysts of 0.01-2.0wt%, (e) one or more photoinitiators of 0.01-10wt%, (f) one or more photosensitizers of 0-10wt%, and (g) 0- Stabilizer/processing aid of 10wt%.The non-acrylate copolymer is selected from polyolefin, polyvinyl aromatic hydrocarbon, polyurethane, gathers Carbonic ester, polyester, polyethers and a combination thereof.

The other embodiment of this theme includes appropriate cured liquid comprising: (a) the thickening group of 5-70wt% Point comprising have 5,000 to 1,000,000, is in some embodiments 15,000-250,000, and in still other implementations It is the acrylic acid base polymer of 15,000-100,000 Mw, (b) the thickening component of 5-70wt% comprising have in mode 1,000 to 500,000, it is in some embodiments 1,000-100,000, and be 1,000- in still other embodiments The non-acrylic acid base polymer of 50,000 Mw, the non-acrylic acid base polymer are selected from polyolefin, polyvinyl fragrance Hydrocarbon, polyurethane, polycarbonate, polyester, polyethers and a combination thereof, (c) one or more structure diluents of 5-80wt%, (d) 0- One or more free radical addition diluents of 40wt%, (e) one or more external catalysts of 0-5.0wt%, (f) 0- One or more photoinitiators of 10wt%, (g) one or more photosensitizers of 0-10wt%, and (h) 0-10wt%'s is steady Determine agent/processing aid.

The other embodiment of this theme includes appropriate cured liquid comprising: (a) the thickening group of 5-50wt% Point comprising have 5,000 to 1,000,000, is in some embodiments 15,000-250,000, and in still other implementations It is the acrylic acid base polymer of 15,000-100,000 Mw, (b) the thickening component of 5-50wt% comprising have in mode 1,000 to 500,000, in some embodiments for 1,000 to 50,000 Mw non-acrylic acid base polymer, it is described non- Acrylic acid base polymer is selected from polyolefin, polyvinyl aromatic hydrocarbon, polyurethane, polycarbonate, polyester, polyethers and a combination thereof, (c) one or more structure diluents of 50-95wt%, (d) one or more external catalysts of 0.01-10wt%, (e) 0- One or more photosensitizers of 10wt%, and (f) stabilizer/processing aid of 0-10wt%.

The other embodiment of this theme includes appropriate cured liquid comprising: (a) 70-80 weight percent Be thickened component comprising with 15,000-250,000 and in some embodiments be 18,000-70,000 Mw propylene Acid copolymer, (b) one or more structure diluents of 15-20wt%, (c) one or more photosensitive initiations of 0.01-5wt% Agent, and (d) stabilizer/processing aid of 0-10wt%.

The other embodiment of this theme includes appropriate cured liquid comprising: (a) the thickening group of 5-15wt% Point comprising have 5,000 to 1,000,000, is in some embodiments 15,000-250,000, and in still other implementations It is the acrylic acid base polymer of 15,000-100,000 Mw, (b) the thickening component of 5-15wt% comprising have in mode 1,000 to 500,000, it is in some embodiments 1,000-100,000, and be 1,000- in still other embodiments The non-acrylic acid base polymer of 50,000 Mw, the non-acrylic acid base polymer are selected from polyolefin, polyvinyl fragrance Hydrocarbon, polyurethane, polycarbonate, polyester, polyethers and a combination thereof, (c) one or more structure diluents of 45-60wt%, (d) One or more free radical addition diluents of 30-40wt%, (e) one or more external catalysts of 0.01-2.0wt%, (f) one or more photoinitiators of 0.01-10wt%, (g) one or more photosensitizers of 0-10wt%, and (h) 0- Stabilizer/processing aid of 10wt%.

The other embodiment of this theme includes appropriate cured liquid.The liquid includes (a) thickening of 5-70wt% Component comprising the non-acrylic acid base polymer with 5,000 to 1,000,000 Mw, the non-acrylic acid base polymer Object is selected from polyolefin, polyvinyl aromatic hydrocarbon, polyurethane, polycarbonate, polyester, polyethers and a combination thereof；(b) 0-40wt% is extremely A kind of few structure diluent；(c) at least one free radical addition diluent of 30-95wt%；(d) solidification of 0-10.0wt% Agent；(e) photosensitizer of 0-10wt%；(f) stabilizer of 0-10wt%.

The another embodiment of this theme includes the method that solidified pressure-sensitive sticks agent.Specifically, solidified pressure-sensitive is glutinous The method of agent includes providing appropriate cured pressure-sensitive adhesive agent, and the pressure-sensitive adhesive agent includes the thickening component of 20-80wt%, Acrylic acid base polymer including the Mw with 5,000 to 1,000,000, at least one structure diluent of 5-50wt%, At least one free radical addition diluent of 10-80wt%, the crosslinking agent of 0-10.0wt%, the first curing agent of 0-4.0wt%, The second curing agent of 0.01-10wt% and stabilizer/processing aid of 0-10.0wt%.This method further includes keeping adhesive sudden and violent The first stimulation of dew or experience selected from radiation, heat, moisture, pressure, ultrasound, Chemical exposure and a combination thereof.

The another embodiment of this theme includes appropriate cured pressure-sensitive adhesive agent comprising the tool of (a) 50-80wt% There is the acrylic acid base polymer of the Mw of 250,000-750,000；(b) at least one structure diluent of 10-30wt%；(c) At least one metal chelate crosslinMng agent of 0-0.5wt%；(d) curing agent of 0-2wt%；(e) stabilization of 0.1-10wt% Agent/processing aid.

As it will be realized, theme as described herein can be realized other and different embodiments, and its is several thin Section is able to carry out the improvement of various aspects, all without departing from claimed theme.Therefore, drawing and description are considered as It is schematical and not restrictive.

Detailed description of the invention

Fig. 1 depicts the dynamic mechanical analysis of the certain embodiments of appropriate cured pressure-sensitive adhesive agent in embodiment 3.

Fig. 2 depicts the general adhesive method of this theme.

Fig. 3 depicts the program of the lap shear test (Lap Shear Test) of embodiment 34.

Fig. 4 depicts the program of the lap shear test of embodiment 35.

Fig. 5, which is depicted, applies the schematic diagram that liquid suitably solidifies liquid to substrate and then by being exposed to actinic radiation.

Fig. 6 is the schematic flow chart for describing the adhesive method according to this theme.

Detailed description of the invention

In some embodiments, the appropriate cured adhesive of this theme includes that (i) is thickened component, can be propylene Acidic group or non-acrylic or including acrylate and non-acrylate combination, (ii) one or more structure dilutions Agent, (iii) one or more free radical addition diluents, and (iv) one or more additives, such as (a) crosslinking agent, (b) are urged Agent such as thermocatalyst and base catalyst, (c) photoinitiator comprising radical photosensitive initiator, UV radical photosensitive Initiator and I and II type photoinitiator, (d) include dyestuff photosensitizer, and (e) stabilizer or processing aid.Following The general introduction of the selection of visible three kinds of main components (i)-(iii) in table 1.

Table 1: the exemplary lists of the main component of composition

There is provided herein the details of these different components.

It is thickened component

Thickening group is broadly defined herein is divided into the molecular weight (Mw) at least 25,000 dalton.It is thickened component (one Kind is a variety of) it can be in some embodiments 20-80wt%, and be in still other embodiments with 10-90wt% 30-70wt%, optionally 5-70wt%, optionally 40-60wt%, optionally 30-50wt%, optionally 5-15wt%, optional The amount of ground 10-15wt% or 80wt% are present in the composition of this theme.Thickening component can be the thickening group of acrylic Point or non-acrylic thickening component.Can be used these and potentially with the combination of other components.Thickening component can have 5,000 to 1,000,000, it is in some embodiments 15,000-250,000, and be 15 in still other embodiments, 000-100,000, optionally 1,000 to 500,000, it is 1,000-100,000 in certain forms, and in still other forms It is 1,000-50,000, or optionally 18,000-70,000 molecular weight (Mw).

In the certain embodiments of this theme, the thickening component of specific acrylic can use as follows.It should be appreciated that This theme includes any acrylate monomer pointed out of substitution, oligomer or component, or in addition, uses corresponding methyl Acrylate monomer, oligomer or component.

MJZ4-87-1: thickening component.The thickening component is the second of 2-EHA by 55wt%, 25wt% The Additol of vinyl acetate, the methyl acrylate of 18wt% and 2wt%^TMThe number-average molecular weight with 50k of S-100 composition (Mn) the atactic propene acid copolymer of (polydispersity index (PDI) 3.5, random copolymer).

MW1-65: thickening component.The thickening component is the acrylic acid of 2-EHA by 50wt%, 48wt% The Additol of methyl esters and 2wt%^TMThe atactic propene acid of the Mn (PDI 3.5, random copolymer) with 50k of S-100 composition is total Polymers.

MW1-69: thickening component.The thickening component be by the 2-EHA of 44.9wt%, 43.1wt% third The Elvacite of e pioic acid methyl ester 43.1%, 10.2wt%^TMThe Additol of 1020 (pMMA) and 1.8wt%^TMThe tool of S-100 composition There is the atactic propene acid copolymer of the Mn (PDI 3.5, random copolymer) of 50k.

MW1-91: thickening component.The thickening component is the second of 2-EHA by 56.1wt%, 25.5wt% Vinyl acetate, 18.4wt% methyl acrylate composition the Mn (PDI 3.5, random copolymer) with 50k atactic propene Acid copolymer.

MW1-93 (most preferred embodiment of synthesis is MW1-101).The thickening component is the acrylic acid 2- ethyl by 55wt% Own ester, the vinyl acetate of 25wt%, the methyl acrylate of 18wt%, 2wt% glycidyl ethacrylate composition The atactic propene acid copolymer of Mn (PDI 3.5, random copolymer) with 50k.

MW1-94: thickening component.The thickening component is acrylic acid and the adduct of MW1-93, and it includes the MW1- of 98wt% Glycidyl methacrylate and chromium (3+) catalyst of 93 and 2wt%.

The Detailed composition for the certain thickening components being presented in table 1 is illustrated in following table 2.

Abbreviation in aforementioned table 2 includes: BA: butyl acrylate；2-EHA: 2-EHA；TBA: tert-butyl Acrylate；EOEOEA: ethoxyethoxy ethyl acrylate；PPO: polypropylene oxide, BMA: butyl methacrylate.

Free radical addition diluent

Free radical addition diluent is with the molecular weight (Mw) for being generally less than 25,000 and/or generally with low at 25 DEG C In the monomer of the acrylic of the viscosity of 25,000cps.Free radical addition diluent is in sometimes referred to as reactivity dilution herein Agent.Free radical addition diluent is in some embodiments 50-70wt% with 10-80wt%, optionally 10-60wt%, can Selection of land 5-70wt%, optionally 0-40wt% be 30-40wt% in still other embodiments, or optionally 7-25wt% Amount is present in the composition of this theme.Free radical addition diluent may include (methyl) acrylate monomer and in certain shapes There is total Mw less than 10,000 dalton in formula.The example of free radical addition diluent useful herein includes ACE, different hard Lipidol acrylate, acrylic acid heptadecane base ester, acrylic acid bicyclopentadiene ester, THF acrylate, alkoxylate THF propylene Acid esters, hydroxy-ethyl acrylate, phenoxyethyl acrylate, urethaneacrylates (Mw < 2000), OXE-10, OXE- 30, S-100, V2100, alicyclic V2100 and PAMA.The many in these components is described in more detail herein in conjunction with example.Below The example of several free radical addition diluents is illustrated in detail.

Alkoxylate THF acrylate is the low viscosity monofunctional monomer that can be used as CD-611 obtained from Sartomer, Middle n is not disclosed, and it is shown as formula (1) as follows:

Hydroxy-ethyl acrylate: the free radical addition diluent is shown as formula (2) as follows:

Phenoxyethyl acrylate: the free radical addition diluent is shown as formula (3) as follows:

The low viscosity monofunctional monomer can be used as SR339 obtained from Sartomer.

Acrylic acid tetrahydrofuran ester (THFA or THF acrylate): the free radical addition diluent is shown as formula as follows (4).The low viscosity monofunctional monomer can be used as SR285 obtained from Sartomer.

Structure diluent can be present in the composition of this theme with following amount: 5-80wt%, optionally 5- 50wt% is in some embodiments 10-50wt%, optionally 5-40wt%, optionally 10-30wt%, optionally 20- 40wt%, optionally 65-95wt%, optionally 75-85wt%, optionally 75-95wt%, optionally 7-25wt%, optionally 45-65wt%, optionally 45-60wt%, optionally 75-85wt% and optionally 15-20wt%.Structure diluent has herein When referred to as structural constituent.Various structure diluents and details are described in conjunction with the embodiments herein.

Various structure diluents include following: trimethylolpropane trimethacrylate (TMPTA).The monomer can be used as SR351 is shown as formula (5) obtained from Sartomer as follows:

Tri (propylene glycol) diacrylate can be used as SR306 obtained from Sartomer, and be shown as formula (6) as follows:

Ethoxylation (3mol) bisphenol a diacrylate.The monomer can be used as SR349 obtained from Sartomer, wherein n+m =3, and it is shown as formula (7) as follows:

Ethoxylation (3mol) trimethylolpropane trimethacrylate, and it is shown as formula (8) as follows:

The monomer can be used as SR454 obtained from Sartomer.

Bisphenol A diglycidyl ether diacrylate is shown as formula (9) as follows:

The monomer can be used as Ebecryl 600 obtained from Cytec.

Radical structure component includes one or more curable materials comprising the homopolymer with Tg > 0 DEG C.It is this Suitable component includes trimethylolpropane trimethacrylate (TMPTA), ethoxylation (x mol) bisphenol a diacrylate, second Oxygroup (x mol) trimethylolpropane trimethacrylate and bisphenol A diglycidyl ether diacrylate.Value x be from 1 to 10, it is in some embodiments from 1 to 5, and be 3 in still other embodiments.

Open loop structure component may be alternatively used in certain embodiments.Suitable open loop structure component include S-21, S-28, Epon 828、Epon 834、A-186 andA-187.It is also useful for epoxy, oxetanes, Acid anhydride and lactams.

The monomer of cationically polymerizable includes material, alkyl vinyl ether, cyclic ethers, styrene, divinyl comprising epoxy Base benzene, vinyltoluene, N- vinyl compound, 1- alkyl alkene (alpha-olefin), lactams and cyclic acetal.

It is known experience cationic polymerization by the material comprising epoxy that the catalysis system of the theme is curable or polymerize Those of, and (1,2- epoxides, 1,3- epoxides are also named as including 1,2- cyclic ethers, 1,3- cyclic ethers and Isosorbide-5-Nitrae-cyclic ethers With 1,4- epoxides).1,2- cyclic ethers is used for certain forms of this theme.

It is included in Frisch and Reegan, Ring-Opening according to the polymerizable cyclic ethers of the theme Polymerizations, described in volume Two (1969) those.Suitable 1,2- cyclic ethers is the epoxidation of monomer and aggretion type Object.They can be aliphatic, alicyclic, aromatics or heterocycle, and will usually have from 1 to 6 and in certain embodiments In be 1 to 3 epoxide equivalent.It is especially useful that aliphatic, alicyclic and diglycidyl ether type 1,2- epoxides, such as ring Ethylene Oxide, epichlorohydrin, styrene oxide, vinylcyclohexene oxygen, vinyl cyclohexene dioxide, glycidol, oxidation fourth two Alkene, the glycidol ether of bisphenol-A, cyclohexene oxide, 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylate, 3,4- Epoxy -6- methylcyclohexylmethyl -3,4- epoxy -6- methylcyclohexanecarboxylic acid ester, bis- (3,4- epoxy -6- methylcyclohexyl first Base) adipic acid, bicyclopentadiene dioxide, epoxidized polybutadiene, 1,4- butanediol diglycidyl ether, phenol formaldehyde (PF) first rank The polyglycidyl ether of phenolic resin or novolac resin, resorcinolformaldehyde resin and epoxysilicone, for example, tool There is the dimethyl siloxane of cycloaliphatic epoxides or glycidyl ether group.

Various commercial epoxy resins are available and in Lee and Neville, Handbook of Epoxy Resins, (1967) and in P.Bruins, Epoxy Resin Technology it is listed in (1968).According to the generation that the theme is polymerizable Table 1,3- and 1,4- cyclic ethers is oxetanes, bis- (chloromethyl) oxetanes of 3,3- and tetrahydrofuran.

In particular, the cyclic ethers being easy to get includes propylene oxide, oxetanes, epichlorohydrin, tetrahydrofuran, Oxybenzene second Alkene, cyclohexene oxide, vinylcyclohexene oxygen, glycidol, octylene oxide, phenyl glycidyl ether, 1,2- oxidation butane, Glycidol ether (for example, Epon 828 and DER 331), the vinyl cyclohexene dioxide (for example, ERL-4206), 3 of bisphenol-A, 4- epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylate (for example, ERL-4221), 3,4- epoxy -6- methylcyclohexyl first Base -3,4- epoxy -6- methylcyclohexanecarboxylic acid ester (such as ERL-4201), bis- (3,4- epoxy -6- methylcyclohexylmethyls) oneself Diacid (for example, ERL-4299), the aliphatic epoxy resin (for example, ERL-4050 and ERL-4052) of polypropylene glycol modified, two Aoxidize cinene (for example, ERL-4269), epoxidized polybutadiene (for example, Oxiron 2001), silicone epoxy (example Such as, Syl-Kem 90), 1,4-butanediol diglycidyl ether (for example, Araldite RD-2), formaldehyde phenolic resin varnish Polyglycidyl ether (for example, DER-431), Epi-Rez521 and DER-438), resorcinolformaldehyde resin (for example, Kopoxite), polyglycols dicyclic oxide (for example, DER-736), polyacrylate epoxides are (for example, Epocryl U- 14), urethane-modified epoxides (for example, QX3599), multifunctional flexible epoxies (for example, Flexibilizer 151) and its mixture and itself and also known to help the mixture of curing agent, curing agent or curing agent (Lee and Neville and Bruins that see above).The curing agent that helps of workable representative curing agent is acid anhydrides such as methyl Carbic 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 is not limited to the material for including epoxy, alkyl vinyl Ether, cyclic ethers, styrene, divinylbenzene, vinyltoluene, N- vinyl compound, cyanate, 1- alkene (alhpa olefin), interior acyl Amine and cyclic acetal.

On the 4th column of U.S. Patent number 5,252,694, the 30th row to the 34th row of the 5th column describes other cationically polymerizable Monomer.The specific monomer of the type includes828, andThe ERL system of 1001F and cycloaliphatic epoxy monomer Column are such asOrThe monomer being particularly useful is ERL series, because of their lower solidification temperature Degree.

Certain lactones can be used for this theme.The lactone that can be used as comonomer in this theme includes shown below as formula (10) those of-(12):

Wherein n is 4 or 5, and h, i, k and m independently are 1 or 2, and each R independently selected from H or includes at most 12 carbon The alkyl of atom.Specific lactone is that wherein R is those of hydrogen or methyl, and the lactone being particularly useful in some embodiments Be e- caprolactone, d- valerolactone, glycolide (1,4- dioxane -2,5- diketone), 1,5- Dioxepane -2- ketone and 1,4- dioxane -2- ketone.

The another type of diluent that can be used for this theme is ring-opened monomer diluent.In the item of the free radical polymerization of use This diluent and other reactants are also non-reacted under part, and it can form acrylate during curing schedule Through going through open loop after polymer.This open loop diluent includes but is not limited to pass through the following general formula for being shown as (13)-(16) as follows Lactone, lactams, cyclic ethers and the cyclosiloxane of expression:

In formula (13)-(16), x range is from such as 3 to 11, and the 3-6 alkylidene group in certain forms.

U.S. Patent number 5,082,922 describes ring-opened monomer and is used for from ethylenically unsaturated monomers as diluent without molten Dosage form is at polymer.But the one-step reaction that patent describes monomer together with open loop diluent.This is different from this theme The two-step Taylor-Galerkin of certain methods provides polymer being initially formed from ethylenically unsaturated monomers, then there is therefore shape At polymer in the case where solidify diluent.The patent referred to provides the use of such as at least 150 DEG C of reaction condition of temperature, It supports two reactions in single step.

Useful ring-opened monomer diluent include but is not limited to butyrolactone, valerolactone, caprolactone, methyl-butyrolactone, in fourth Amide, valerolactam, caprolactam and siloxanes.

A kind of siloxanes ring-opened monomer isA-186 serves as open loop by silane-silane condensation reaction The structural constituent of consolidated structures component and silane-functional.A-186 (β (3,4- epoxycyclohexyl) ethyl front three Oxysilane) there are following formula (17):

Although polymerization reaction can be carried out there are non-reactive solvent, which can be substantially solvent-free In the case where advantageously occur.In some embodiments, solvent will be with by weight at most about percent 10, and preferably not Amount greater than by weight percent 5 exists, this total weight based on reactant.Solvent can be from the product of diluent reaction step It removes (for example passing through heating).Exemplary non-reactive solvent includes ketone, alcohols, esters and hydrocarbon solvent, such as ethyl acetate, Toluene and dimethylbenzene.

For this themeOxazoline orOxazolidine includes having those of following formula (18)-(19):

Wherein R indicates the branching comprising 5 to 8 carbon, saturation aliphatic alkyl.It is another suitableAzoles woods shows as follows It is shown as (20):

Wherein R indicates the branching comprising 5 to 8 carbon, saturation aliphatic alkyl.

It is useful hereinOxazolidine mixture usually has at 23 DEG C less than 8,000mPa.s, and is less than in certain forms Therefore 6,500mPa.s viscosity is suitable as the solvent-free curing agent of the polymer precursor comprising isocyanate groups.With packet Polymer precursor composition containing isocyanate groups, they are suitable for the production of solvent-free or low solvent, one-component system, fit again Cooperation is the adhesive of high quality mould coating, coating composition or sealing compositions.These systems are usually by being exposed to atmospheric moisture Degree is cured after the application.The polymer precursor comprising isocyanate groups suitable for producing these systems is included in such as U.S. Organic polyisocyanates described in the patent No. 4,002,601 or isocyanate prepolymer.Generally, in U.S. Patent number 5, It is described in 189,176 useful hereinOxazoline.

In some embodiments, bismaleimide can be used.The bismaleimide that can be used for this theme is to include The organic compound of two maleimide base groups, and generally prepared by maleic anhydride and diamine.It can be by following General formula (21) describes bismaleimide:

Wherein R³It is divalent aromatic or alicyclic organic group.In certain forms, useful bismaleimide is originated from Aromatic diamine, and especially wherein R³It is those of polynuclear aromatic base.The example of this bismaleimide includes 2,2- Bis- (4- amino-benzene oxygen -4- phenyl) propane bismaleimide, bis- (3- amino-benzene oxygen) the diphenyl sulphone (DPS) bismaleimides of 4,4'- Bis- (3- aminophenyl isopropylidene) the benzene bismaleimide of amine, 1,4- and bis- (4- aminophenyl) methane bismaleimide. Bismaleimide can be used either individually or as mixture.

It is also possible to using such bismaleimide, wherein the at most 50% substituted horse of maleimide base group Come imide group such as methylmaleimido or halomalonimide or sub- by nadikimide, methyl nadik acyl Amine or different maleimide base group substitution.It the part of maleimide base group can also be by succinimide, phthalimide Or succinimide and phthalimide-based the group substitution replaced.

Bismaleimide can be prepared by many well known methods by maleic anhydride and diamine, and many can be easy Ground is obtained from commercial source.

As previously mentioned, in some aspects of this theme, one or more components of composition such as thickening group Dividing can be with the thickening component of right and wrong acrylic.The component of various non-acrylics can be used.Non-limiting example packet Include polyolefin, polyvinyl aromatic hydrocarbon, polyurethane, polycarbonate, polyester, polyethers and these combination, and it is possible in conjunction with One or more other reagents and/or component.The specific non-limiting example of polyethylene aromatics is polystyrene.

Additive

Various additives and initiator combine the adhesive of this theme and composition is useful.Sometimes, art is used herein Language " curing agent ".The term refers to that the reagent for the polymerization for promoting or causing polymer in theme composition (one or more) is (a kind of Or a variety of) or stimulation.Therefore, term curing agent includes the group of single reagent, single stimulation, plurality of reagents, a variety of stimulations, reagent It closes, the combination of the combination of stimulation and one or more reagents and one or more stimulations.In general, curing agent is (a kind of or more Kind) can be activated, i.e., by radiation, heat, moisture, pressure, ultrasound, be exposed to chemical reagent and at least one of a combination thereof can quilt Activation.In general, as used herein term curing agent refers to catalyst and/or photoinitiator.It should be appreciated, however, that should Term may include other various reagents (and stimulation).

Thermocatalyst.Catalyst can be external or internal herein.Catalyst can be with 0-10wt%, 0.1- The amount of 10wt%, 0-5wt%, 0.1-5wt%, 0-4wt%, 0.1-4wt%, 0-2wt%, 0.1-2wt% or 0.01-2wt% It uses.Suitable catalyst includes end-sealed type strong acid catalyst, based on acid consisting of the following, such as trifluoromethanesulfonic acid (triflic acid), dinonylnaphthalene sulfonic acid (DSA), dinonylnaphthalene disulfonic acid (DDSA), hexafluorophosphoric acid and lithium ammonium antimony (road Lewis acid), and it is available from KingIndustries, such asCXC1615 (diethylamine salt of trifluoromethanesulfonic acid),155 (the end-sealed type acid catalysts based on DNNDSA),CXC 1612 (lithium ammonium antimony),Super-A218 (zinc salt of trifluoromethanesulfonic acid),CXC 1738 (ammonium hexafluorophosphate) and CXC1614 (trifluoromethanesulfacid acid ammonium).

Base catalyst can be primary amine, secondary amine or tertiary amine.Suitable primary diamines are diaminodiphenylsulfones.Other alkali include miaow Azole and ketimide.Suitable imidazoles include 2-methylimidazole, 2- ethyl 4-methylimidazole, 2- phenylimidazole.It is special in the U.S. The list of sharp 200,9/0,194,320 section of visible imidazole curing agent of application publication number.Possible alkaline curing agent is dicyandiamide [DICY]。

Photoinitiator.Photoinitiator includes radical photosensitive initiator and UV radical photosensitive initiator.It is photosensitive to draw Hair agent can be present in the composition of this theme with the amount of 0-10wt%, 0.01-10wt%, 2-5wt% or 1-3wt%.

Radical photosensitive initiator.Thermal initiator includes peroxide -2 ethyl hexanoic acid tert-butyl ester, the tertiary fourth of peroxidating neopentanoic acid Ester, peroxide -2 ethyl hexanoic acid tert-pentyl ester, benzoyl peroxide, peroxide acid tert-amyl acetate, peroxide acetic acid butyl ester and The azo-compound sold with trade (brand) name Vazo such as Vazo 52, Vazo 67 and Vazo 88.

UV radical photosensitive initiator.The photoinitiator for being suitable for this theme includes I type and II type photoinitiator two Person.

I type photoinitiator is defined as substantially undergoing unimolecule bond cleavage reaction once irradiating, thus the base that gains freedom. Suitable I type photoinitiator is selected from benzoin ether, benzil ketals, α-dialkoxy-acetophenone, Alpha-hydroxy alkyl phenyl ketone And acyl-phosphine oxides.Suitable I type photoinitiator is commercially available, such as obtained from Lamberti Spa, Gallarate, Italy, Esacure KIP 100, or obtained from Ciba-Geigy, Lautertal, Germany's Irgacure651。

In general, suitable I type photoinitiator compound is selected from benzoin ether, benzil ketals, α-dioxane herein Oxygroup-acetophenone, Alpha-hydroxy alkyl phenyl ketone and acyl-phosphine oxides.

II type photoinitiator is defined as substantially undergoing bimolecular reaction, and wherein photoinitiator is under excited state It interacts with the second compound for serving as aided initiating to generate free radicals.Suitable II type photoinitiator is selected from hexichol first Ketone, thioxanthones and titanocenes.Suitable aided initiating is preferably chosen from amine functional monomer, oligomer or polymer, thus amino Functional monomer and oligomer are used in certain embodiments.Primary amine, secondary amine and tertiary amine can be used, thus tertiary amine is used for certain In a little embodiments.Suitable II type photoinitiator is commercially available, such as obtained from Lamberti Spa, The Esacure TZT of Gallarate, Italy, or obtained from Aldrich Co., Milwaukee, Wisconsin, the 2- of USA Or 3- methyl benzophenone.Suitable amine aided initiating is commercially available, such as obtained from Rahn AG, Zurich, Switzerland's5275。

The specific example of II type photoinitiator compound includes benzophenone and thioxanthones.In specific embodiment In, aided initiating compound such as amine may exist and can interact with II type photoinitiator compound.

Crosslinking agent.Crosslinking agent useful herein includes the crosslinking agent of radiation activatable, is selected from aldehydes, ketone, quinones, thiophene Ton ketone and s-triazine.Metal chelate crosslinMng agent catalyst is also expected.Crosslinking agent can be with 2 to 95wt%, 0- 4wt%, 0.01-4wt%, 0.01-2wt%, 0-2wt%, 0.01-1wt%, 0-1wt%, 0.01-0.5wt% or 0- The amount of 0.5wt% is present in the composition of this theme.

Photosensitizer.Every kind of sensitizer tends to ring in visible light and ultraviolet spectrum with the feature of itself It answers, they can be applied in combination to expand the light of response in this way, and/or increase the response speed for being exposed to light.

Photosensitizer can with such as 0-15wt%, 0.01-15wt%, 0-10wt%, 0.01-10wt%, 0-5wt%, The amount of 0.01-5wt%, 0-2wt%, 0.01-2wt%, 0-1wt% and 0.01-1wt% are used for the composition of this theme.It is photosensitive Agent can be sensitizing dye.

Schematic sensitizing dye is those of in following classifications: diphenyl methane, xanthene, acridine, methine and polymethine, The aminostyryl chemical combination that thiazole, thiazine, azine, amino ketones, porphyrin, colored aromatic polycyclic hydrocarbons, thioxanthones, p- replace Object and aminotriaryl methanes.

Stabilizer and processing aid.The stabilizer and processing aid of several classifications are it is contemplated that including oil/wax, anti-oxidant Agent, photosensitizer, rheology modifier, filler, radical structure component, open loop structure component, epoxy resin, oxetanes, acid anhydride, Lactams, lactone,Oxazoline, isocyanates, bismaleimide and azo dioxide (azodioxide).Stabilizer and plus Work auxiliary agent is used for the amount of such as 0-10wt%, 0.1-10wt%, 0-4wt%, 0.1-4wt%, 0-3wt% and 0.1-3wt% In the composition of the theme.In some embodiments, it is useful for using azo dioxide as stabilizer.Such one A example is to be available commercially from Hampford Research, the entitled UVTS-52's of Inc.of Stratford, CT Stabilizer.UVTS-52 is the azo dioxide of thermal reversion.UVTS-52 (CAS 34122-40-2) is considered as 1,4,4- tri- Methyl -2,3- diazabicyclo-[3.2.2]-nonyl- 2- alkene -2,3- dioxide.

Plasticizer-oil and wax.Suitable plasticizer includes plasticising oil, such as mineral oil, but there are also olefin oligomer and The derivative of low-molecular weight polymer or glycol benzoate and vegetable oil and animal oil and this kind of oil.Workable derivative It is the opposite higher boiling material temperature comprising the only aromatic hydrocarbon of small scale from the oil of petroleum.In this regard, in certain embodiments Middle aromatic hydrocarbon should be based on the weight of oil less than 30%, and more specifically less than 15%.Optionally, oil can be fully non-aromatic Race.The suitable oligomer for including as plasticizer can be polypropylene, polybutene, hydrogenated polyisoprene, hydrogenation fourth two Alkene or the like has the average molecular weight between about 100 and about 10,000g/mol.Suitable vegetable oil and animal oil Glycerine esters including common fats sour (for example, stearic acid, oleic acid, linolenic acid, linolenic acid) and its polymerization product.It can make With other plasticizer, condition is that they have suitable compatibility.Have also been discovered that the ring manufactured by Nynas Corporation Alkane mineral oil222B is suitable plasticizer.It arrives as will be appreciated, plasticizer is normally used for reducing whole adhesive The viscosity of composition, and do not reduce the use temperature of adhesive strength and/or adhesive substantially.The selection of plasticizer is specific It is useful in the formula of final use (such as wet strength core application).Because be related to production and material cost it is economical because Element, since the cost of plasticizer is usually less than the other materials of such as polymer and tackifying resin in formula, for cost Consider, the amount of plasticizer should maximize in adhesive.

Wax can also be combined with the amount of by weight 0% to 20% or 0.1-20wt% or 0.1-15wt% for adhesive Object, and for reducing the melt viscosity of adhesive, and insignificantly reduce its adhesive bonding feature.These waxes are also used for dropping The open assembly time of low composition, without influencing temperature performance.

The example of useful wax material includes following.

May use with as by ASTM method D-1321 measure from about 0.1 to 120 hardness number and from about 66 DEG C To low molecular weight (100-6000g/mol) polyethylene of 120 DEG C of ASTM softening points.

May use pertroleum wax, such as the paraffin with the fusing point from about 130 °F to 170 °F and with from about 135 °F to The microwax of 200 °F of fusing point, the latter's fusing point are measured by ASTM method D 127-60.

The random polypropylene with the ring and ball softening point from about 120 ° to 160 DEG C may be used.

It may use through Clariant International, Ltd., Muttenz, the commercialized name of Switzerland The referred to as propylene type wax of the metallocene catalysis of " Licocene ".

The wax of metallocene catalysis or the wax of single site catalysed may be used, such as in 4,914,253 He of United States Patent (USP) Described in 6,319,979 and WO 97/33921 and WO 98/03603 those.

Paraffin, microwax, polyethylene wax, polypropylene wax, by-product polyethylene wax, by polymerizeing carbon monoxide may be used With synthetic wax such as Fischer-Tropsch (Fischer-Tropsch) wax, oxidized Fischer-Tropsch wax, functionalized waxes and its mixture of hydrogen manufacture.

Polyolefin-wax.As used herein, term " polyolefin-wax ", which refers to, those of forms polymer by olefin monomer unit Or long-chain entity.These materials are commercially available with trade (brand) name " Epolene " from Westlake Chemical Co..

There is 200 °F to 350 °F of ring and ball softening point for the material in the certain embodiments of this theme.Such as should Understand, each in these waxes is solid at room temperature.Other useful substances include hydrogenated animal, fish and plant fat and Oil, such as hydrogenated tallow, lard, soya-bean oil, cottonseed oil, castor oil, herring oil, cod-liver oil etc., and since they are hydrogenated, institute With at ambient temperature they be solid, find its about be used as wax material equivalent be useful.These hydride materials are usual It is referred to as " animal or plant wax " in adhesive industry.

Antioxidant.Adhesive also generally includes about 0.1% to about 5% stabilizer or antioxidant.In this theme Useful stabilizer is incorporated into help to protect above-mentioned polymer in Adhesive composition, and to protect entire glue Not heated and oxidative degradation the influence of glutinous agent system, heat and oxidative degradation usually during the manufacture of adhesive and application and Final product often just is being exposed to occur in atmospheric environment.This degradation is usually special by the appearance of adhesive, physical characteristic and performance The deterioration of sign is proved to.In some embodiments, the antioxidant being particularly useful is manufactured by Ciba-Geigya Irganox 1010 --- four (methylene (3,5- di-tert-butyl-4- hydroxy hydrocinnamate)) methane.Applicable It is high molecular weight hindered phenols and multifunctional phenols, such as the phenols of sulfur-bearing and phosphorus in stabilizer.Hindered phenol is to those skilled in the art Member is well known, and being characterized by also is including steric bulk group (sterically bulky close to its phenolic hydroxyl group Radicals phenolic compound).In particular, tertiary butyl groups generally on phenyl ring relative at least one ortho position of phenolic hydroxyl group at It is substituted.In hydroxyl adjacent place, the presence of these steric bulk substituent groups is used to prevent its stretching frequency, and correspondingly Prevent its reactivity.Therefore the steric hindrance provides its stability characteristic (quality) for phenolic compound.Representative hindered phenol includes:

1,3,5- trimethyl -2,4,6- three (3-5- di-tert-butyl -4- hydroxyphenyl) benzene；

Four -3 (3,5- di-tert-butyl -4- hydroxyphenyl) propionates；

N-octadecane base -3 (bis- tert-butyl -4- hydroxyphenyl of 3,5-) propionic ester；

4,4' methylene bis (4- methyl-6-tert-butylphenol)；

4,4'- thiobis (6- tert-butyl-o-cresol)；

2,6- di-tert-butylphenol；

Bis- (just pungent the sulfenyl)-l of 6- (4- hydroxyphenoxy) -2,4-, 3,5- triazine；

2,4,6- tri- (4- hydroxyl -3,5- di-tert-butyl-phenoxy)-l, 3,5- triazine；

Two-n-octadecane base -3,5- di-t-butyl -4- hydroxyphenyl phosphates；

2- (just pungent sulfenyl) ethyl -3,5- di-t-butyl -4- hydroxy benzoate；With

Six-(3,3,5- di-t-butyl -4- hydroxy-pheny) propionic acid sorbitol esters.

By being used in combination with following, the performance of these stabilizers can be further improved；(1) synergist, such as example Such as dilauryl thiodipropionate and phosphite ester；(2) chelating agent and metal deactivator, such as, ethylenediamine tetra-acetic acid, Its salt and two the third diimines of salicyloyl (disalicylalpropylenediimine).

Ultraviolet inhibitor.Antioxidant can be used for preventing the oxidative attack to Adhesive composition, can lead to adhesive The loss of the gluing intensity of composition and interior viscous intensity.Useful antioxidant includes but is not limited to amine, for example be can be used as Bis--betanaphthyl of N-N'--Isosorbide-5-Nitrae-phenylenediamine that AGERITE D is obtained, phenolic compound, for example come from Monsanto Chemical Co. 2,5- bis--(tertiary amyl) hydroquinone that can be used as SANTOVAR A acquisition, from making for Ciba-Geigy Corp. For four [3- (3', 5'- di-t-butyl -4'- hydroxyphenyl) propionic acid ethyl] methane that IRGANOX 1010 is obtained, and can be used as The 2-2'- di-2-ethylhexylphosphine oxide (4- methyl-6-tert-butylphenol) and dithiocarbamate that ANTIOXIDANT 2246 is obtained, Such as two thiobutyl carbaminate.

Rheology modifier.Rheology modifier can be added to change the thixotropic behavior of composition.Suitable rheology modifier packet Include polyamide wax, pyrogenic silica, flowing control additive, reactive diluent, anti-settling agent, alpha-olefin, hydroxy-end capped silicon Oxygen alkane-organic copolymer, including but not limited to hydroxy-end capped polypropylene oxide-dimethylsiloxane copolymer and a combination thereof.

Filler.Filler can be used for assigning intensity or reduce totle drilling cost.Filler useful herein includes three aluminium hydroxides, hydrogen-oxygen Change calcium, with trade (brand) nameThe glass marble of expandable microballoon, carbon black, titanium dioxide or the nickel coating sold.

In certain forms of this theme, filler, rheology modifier and/or pigment are present in adhesive.These can hold Several functions of row, for example change the rheological characteristic of adhesive in the desired manner, moisture is absorbed from adhesive or the substrate for applying it Or oil, and/or promote cohesional failure, rather than bond damage.Other examples of this material include calcium carbonate, calcium oxide, cunning Stone, coal tar, textile fiber, glass particle or fiber, aramid fiber slurry, boron fibre, carbon fiber, silicate mineral, mica, powdery Quartz, bentonite, wollastonite, kaolin, pyrogenic silica, aerosil or metal powder such as aluminium powder or iron Powder.In these, calcium carbonate, talcum, calcium oxide, pyrogenic silica and wollastonite are particularly useful, individually or With some combinations, since these generally promote desired cohesional failure mode.

In addition to various concrete compositions as described herein, this theme also provides several specific combinations in addition illustrated as follows Object.It should be appreciated that these are the representativeness of other concrete compositions of this theme, non-limiting example.

The other embodiment of this theme includes appropriate cured pressure-sensitive adhesive agent comprising: (a) 50-80wt% Acrylic acid base polymer with 250,000-750,000 Mw, (b) one or more structure diluents of 20-40wt%, (c) the epoxy functionalized component of optional acrylic acid-of 0-30wt%, (d) metal chelate crosslinMng agent of 0-0.5wt%, and (e) 0- One or more external catalysts of 2wt%.

The another embodiment of this theme is the curable pressure-sensitive adhesive agent formed by blend, wherein the blending Object includes (a) random copolymer of high molecular weight (such as 400-600kg/mol) comprising (i) alkyl acrylate basis is single Body；(ii) vinyl acetate；(iii) methyl acrylate；(iv) acrylic acid；(v) crosslinked with silicane monomer；(b) low molecular weight (example Such as 20-50kg/mol) random copolymer comprising (i) straight acrylic Arrcostab base monomer, (ii) branch alkyl acrylate Base ester base monomer and (iii) epoxy functionalized methacrylate monomers；(c) oligomer is such as from the STPE-30 of Wacker； (d) acrylate-glycidyl esters of 10- carbon carboxylic acid；(e) cationoid reaction diluent, such as trimethylolpropane oxygen Azetidine (TMPO)；(f) high molecular weight acids functional acrylic diluent monomer, (example is 2- acryloxypropyl neighbour's benzene Dicarboxylic acid esters)；(g) bisphenol-A-type epoxy resin is semisolid at room temperature；(h) crosslinking agent and silane catalyst be such as Aluminium acetylacetonate.

This theme be also provided with liquid and composition as described herein for combination methods and techniques.Fig. 2 is schematic Depict the adhesive method 300 according to this theme.In method 300,310 quilt of the layer of composition as described herein or coating It is applied to interested substrate or film 320.Composition can with various technologies such as at operation 330 general description spraying or Coating applies.Then viscosity, such as Fig. 2 is presented by being exposed to such as UV radiation in composition that is being coated with or otherwise applying In shown by 340.In this state, composition is commonly known as " A- stage ", and can show in some embodiments The T- peel value of 0.17lbs and 180 ° of removings of 0.64lbs.The layer of another material layer such as copper and aluminium foil as shown in 350 Then pressure object is contacted with sticky A- phase composition 310.Resulting laminated assembly is related to one or more processing stations such as laser Device pattern forms station 360, forms the figuratum laminate as described in Fig. 2 370.It, can be into depending on final use requirement The removal of the other processing such as foil clout (matrix) of row, for example useless clout 380 is collected at operation 375.It is resulting to add The laminate of work is shown as 385.Then the laminate 385 processed can undergo one or more other process operations, such as aobvious It is shown as 390 heat cure.Those of after heat cure, composition 310 is referred to as " B- stage ", usually show with its A- stage Significant bigger the T- removing and 180 ° of peel values compared.For example, the T- peel value in B- stage can be about 0.37lbs and 180 ° Peel value can be about 3.6lbs.Cured article can be collected with roll form or sheet form 395.

In general, in the various embodiments of this theme, when passing through any reagent as described herein or stimulation When being at least partially cured composition, liquid or composition as described herein can be presented viscosity or show usually and pressure-sensitive adhesive The relevant characteristic of agent.In certain forms, realized by the way that composition is exposed to UV radiation, electron beam, heat or these combination First is cured or partially cured.In addition, by be exposed to heat, the chemical reagent including water or moisture, pressure, or combinations thereof, should Then partially cured composition can further be solidified.

This theme composition can be used for various applications.For example, the application of particular use can be related to by described herein Composition manufacture foamed product.One or more conventional foaming agents can be incorporated into that the composition of this theme, blister Or expansion, to generate froth bed or article.Composition can be also used for adhesively for foamed product being bound to other surfaces, substrate Or object.

More specifically, this theme can be used for combining or otherwise coherent film and film, film and foil, apron and foil, skin Circle and film, fabric and fabric, fabric and substantially any other materials or substrate such as film, paper and metal, paper and metal, metal With the combination of metal, film and other plastics, plastics and plastics and these and other surfaces, material and/or substrate.This theme can It is also used for providing the chemoresistance to various surfaces and substrate, such as anticorrosive.For example, the theme can be used for providing chemical resistance Label and solvent tolerance laminate such as solvent tolerance glass and foil component.This theme can also be used for forming film laminate, such as Film and film laminate.Another expected application of this theme is the field of shrinkage sleeve and shrinkage sleeve label.In addition, this theme It can be widely applied to the solvent welding of two membranes.Still another application field be related to component and especially metal tube such as oil and The corrosion protection of gas pipeline.The composition and method of this theme can be used for providing or increasing anti-impact force, structural intergrity and Protection that is anticorrosive or being exposed to environmental factor.The specific and non-limiting example of this corrosion protection be to provide outer layer, internal layer, Or along both the external peripheral surface of pipe and/or inner circumferential surface.According to another significant benefit of certain compositions of this theme It is that composition can undergo bending, flexure or other stress without cracking.If such as composition (one or more) is applied to Pipeline, this is desired.Still another expected application of certain compositions of this theme is that form glass fibre structure such as extra large Foreign ship body, certain sports goods and structure member.The still another application of this theme is " rolling tightly, tighten " (ROSO) application.

Embodiment

Embodiment 1-4

The appropriate cured adhesive of the certain embodiments of this theme can be described as and reactive diluent, oligomer With the acrylate copolymer of structural constituent mixing.The other details of this theme is provided in the following embodiments.

Embodiment 1: the high-performance PS A with moisture cured oligomer (appropriate cured adhesive)

Embodiment 1 is the acrylate copolymer with the oligomer (STPE-30) of potential reaction.STPE-30 oligomer Pass through silane-silane condensation reaction solidification.Optionally, base polymer can also have silane functionality and can be with reactivity Oligomer coreaction.

Embodiment 2: the high-performance PS A of the oligomer (appropriate cured adhesive) with UV curable

Embodiment 2 is the acrylate copolymer mixed with reactive diluent and structural constituent, is triggered by UV exposure To convert solid PSA from liquid for adhesive, and by being heating and curing during film and film layer pressure to abundant intensity.

In order to which moisture-curable in situ is incorporated to high performance pressure sensitive adhesive system, by acrylate copolymer, tackifier and anti- Answering property oligomer mixes in a solvent.After applying as described herein and being exposed to humidity, leading to a part of oligomer Under conditions of potential reaction, which is applied to belt-like form.

Embodiment 3: the high-performance PS A with moisture cured oligomer (appropriate cured adhesive, solid component)

The composition of embodiment 3 is the high-performance PS A with moisture cured oligomer (appropriate cured adhesive). It is in order to which moisture-curable in situ is incorporated to high performance pressure sensitive adhesive system, acrylate copolymer, tackifier and reactivity is oligomeric Object is mixed in a solvent or is otherwise combined.After applying and being exposed to humidity, causing a part of oligomer potential Under conditions of reaction, which is applied to belt-like form.

Table 3: the composition of embodiment 3PSA

Weight percent	Component
		54.45%	DEV-8631 U (acrylic acid base polymer)
25%	Terpene phenol class tackifier (110-120 DEG C of softening point)
		20%	Terpene phenol class tackifier (110-120 DEG C of softening point)
0.55%	Metallo-chelate pentanedione aluminium (crosslinking agent & catalyst)

Acrylic acid base polymer is high molecular weight (400-600kg/mol) random copolymer comprising (a) alkyl Acid esters base monomer；(b) vinyl acetate；(c) methyl acrylate；(d) acrylic acid；(e) crosslinked with silicane monomer.

The example of acrylic acid base polymer is DEV8631U, is the molecular weight (Mw) with about 518,000g/mol Random copolymer comprising following compositions.

Table 4: the acrylic acid base polymer (i.e. DEV8631U) in embodiment 3PSA

Component	Weight percent
		2-EHA (base monomer)	57.95
Vinyl acetate (modified monomer)	25
		Methyl acrylate	15
Acrylic acid (high Tg monomer, crosslink sites)	3
		Methacryloxypropyl trimethoxy silane (cross-linking monomer)	0.05

Reactive oligomers are silane-terminated polyether (oligomer), for example, be shown as follows formula (22) from Wacker's STPE-30.STPE-30 is silane-terminated polyether.Two Silante terminated polypropylene glycols of display are based on identical polyethers.It is distinguished It is end group.

Crosslinking agent and catalyst are aluminium acetylacetonate and are shown as formula (23) as follows:

Adhesive method is described in Fig. 6.With reference to Fig. 6, it is however generally that, it is as follows according to the combination method 200 of this theme.? In operation 210, composition as described herein is applied or is otherwise applied on film or substrate.The example of this film It is release film.After suitable application, dry compositions, this also typically includes any solvent of at least part in composition Removal, as operation 220 is described.Dry representative of conditions includes being exposed to 80 DEG C for about 5 minutes.In operation 230, so Composition is properly cured by being exposed to heat and/or humidity afterwards, to form high-intensitive adhesive 240.The condensation of generation is anti- It should show as follows:

~Si-OCH₃+H₂O →~Si-O-Si~+CH₃OH

Fig. 1 depicts the dynamic mechanical analysis of the appropriate cured pressure-sensitive adhesive agent of embodiment 3.

Embodiment 4: the curable liquid composition that B-stage is carried out for PSA (UV) and during film and film layer pressure is (appropriate solid The adhesive of change)

In example 4, acrylate copolymer is mixed with reactive addition diluent and structure diluent.

Table 5: the composition of 4 liquid composition of embodiment

Weight percent	Component
		15%	ACE monomer stage component (reactive diluent)
10%	V2100 (reactive diluent)
		10%	Epon 834 (structural constituent)
9%	TMPO oxetanes (structural constituent)
		56%	EB14-04 (acrylate copolymer)

The example of reactive diluent is ACE monomer ACE^TMAcrylic acid hydroxyl ester monomer, by Momentive Performance Materials, Leverkusen Germany are provided, and are acrylic acid and Cardura^TMReaction product.Cardura is Versatic^TMThe glycidyl esters of Acid 10 are the highly branched saturated carboxylic acid comprising 10 carbon atoms.ACE has In conjunction with the unique texture of large volume hydrophobic tail, pendant hydroxyl groups and acrylate-functional groups, molecular weight is about 300.ACE has as follows It is shown as the structure of formula (24):

Another reactant diluent --- high molecular weight acids functional acrylic diluent monomer V-2100, is available From the 2- acryloxypropyl phthalic acid ester of New York San Esters Corporation, it is shown as formula (25) as follows:

Structural constituent is EPON^TMResin 834 is to be available from Momentive Performance Materials It is at room temperature semisolid BPA base epoxy.It can be configured to can be used for various Gao Gu using the system of EPON resin 834 Body and modified by tar coating, Gao Qiangren adhesive, laminated material and preimpregnation moulding material.Because of its higher molecular weight, EPON Resin 834 provides increased system response, adhesive surface and solidified resin toughness compared with liquid grade BPA epoxy resin, but It is reduction of raising temperature performance.EPON resin 834 is in the application for needing additional adhesive surface, curing rate or toughness It is particularly useful.

Another structural constituent is cationoid reaction diluent, such as trimethylolpropane oxetane (TMPO). UV/EB cationic formulation can be formed, and it mainly includes resin, diluent and photoinitiator, for example as Primary resins - 3,4 7-oxa-bicyclo[4.1.0 carboxylic acid of 3,4 epoxycyclohexyl-methyl (being shown as formula (26) as follows) and as reactive diluent TMPO:

Acrylate component is low molecular weight (20-50kg/mol) random copolymer comprising (a) straight acrylic Arrcostab Base monomer, (b) branch alkyl acrylate base monomer and (c) epoxy functionalized methacrylate monomers.

The example of acrylate component is following low-molecular weight polymer EB14-04, is the Mw with about 40,000g/mol Random copolymer:

Table 6: the example of acrylate component, i.e. EB14-04 in 4 liquid composition of embodiment

Component	Weight percent
		Butyl acrylate (base monomer)	40
Tert-butyl acrylate	40
		S-100 (alicyclic epoxy function methacrylate monomers)	30

Adhesive method is described in Fig. 6.

Embodiment 5-7

Embodiment 5-7 illustrates the polymerization of the component and composition that can be used to form this theme.

Embodiment 5: component with intend polymerizeing for distant pawl, using SFRP reagent have epoxy functionalities embodiment

Following preparation has the acrylic copolymer for the active functionality being located in the section adjacent with polymer chain terminal, It is shown as formula (27) as follows:

In the 1500ml reactor feed for being equipped with heating mantle, blender, reflux condenser, head tank and nitrogen inlet Blocbuilder of the 8.30g from Arkema Inc.Monomer and solvent are added into feed containers with following amounts:

22.30g 2-EHA；

64.30g ethoxy ethoxy ethyl acrylate；With

85.30g propyl acetate

Monomer in Blocbuilder and feed containers and solvent in reactor are bubbled with constant nitrogen at room temperature Cleaning 30 minutes.After the holding, monomer and solvent mixture are fed to reactor to generate and living polymer mode The non-reacted section of adjacent fraction, to add acrylate group to Blocbuilder.Reactor feed mixture It is then heated to and is greater than 70 DEG C (75 DEG C of reactor jacket), and keep 30min.After second keeps, reactor feed is mixed It closes object and is cooled to room temperature (about 25 DEG C).Once reactor feed reaches room temperature, by the Synasia Epoxy S-100 of 13.40g It is fed into reactor.After adding the epoxy resin, reactor is sealed, and is bubbled clearly with constant nitrogen at room temperature It washes other 30 minutes.After 30 minutes are bubbled, reactor mixture is heated to 100 DEG C.When reactor mixture is heated When to 100 DEG C, the ethoxy ethoxy ethyl acrylate of 579.10g and the 2-ethylhexyl acrylate of 201.10g are fed To feed containers, and with constant nitrogen pressure pulse cleaning.When reactor mixture reaches 100 DEG C, the time is set as zero (T =0).At T=15 minute, sampling checks that monomer is converted for gas chromatographic analysis.When monomer conversion is identified (about 30 Minute, T=45), reactor mixture is maintained under reflux at a temperature of between 110 DEG C and 117 DEG C, until the epoxy of conversion Resin > 90% (about 70% 2-EHA and EOEOEA conversion).At the conversion, the reagent feeds of active nitrogen cleaning are mixed It closes object and is added into reactor during 180 minutes.During reagent feeds, the temperature of reaction is maintained at 110- under reflux 118℃.After reagent feeds completion, conversion of the reaction condition until realizing 80% 2-EHA and EOEOEA is maintained.This be for The remainder of the generation non-reacted section adjacent with function end segments.At the conversion, the Synasia of 13.40g The propyl acetate of Epoxy S-100 and 13.40g are generated final function end region by quick feeding to reactor (about 2min.) Section.Maintain conversion of the reaction condition until realizing 2-EHA and EOEOEA greater than 98%.Acquired solution polymer is subsequently cooled to Environment temperature and from reactor be discharged.The total theoretical Mn of polymer is 41,000g/mol.Each non-reacted centre portion It is 32,000g/mol and function end segments are 4,500g/mol.

The molecular weight (Mn) of total acrylate copolymer of measurement is 20,043g/mol (by relative to polystyrene mark Quasi- gel permeation chromatography measurement) and polydispersity be 3.02.So the Mw calculated is 60,530g/ moles.

Embodiment 6: with polymerizeing for individual feature end segments (tadpole), there is the implementation of alcohol functionalities using SFRP reagent Example

Following preparation has the acrylic copolymer for the active functionality being located in the section adjacent with polymer chain terminal, It is shown as (28):

In the 1500ml reactor feed for being equipped with heating mantle, blender, reflux condenser, head tank and nitrogen inlet 11.41g Blocbuilder.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 acrylic acid 4- hydroxypropyl acrylate of 17.26g

Monomer in Blocbuilder and feed containers and solvent in reactor are bubbled with constant nitrogen at room temperature Cleaning 30 minutes.After the holding, monomer and solvent mixture are fed to reactor to generate and living polymer mode The reactive section of adjacent fraction, to add acrylate group to Blocbuilder.Reactor feed mixture is right After be heated to greater than 70 DEG C (75 DEG C of reactor jackets), and keep 30min.After second keeps, reactor mixture quilt It is heated to 100 DEG C.When reactor mixture is heated to 100 DEG C, the butyl acrylate of 1071.14g and the tert-butyl of 267.78g Acrylate is fed to feed containers, and with constant nitrogen pressure pulse cleaning.When reactor mixture reaches 100 DEG C, Timer is set as zero (T=0), and is maintained between 100 and 105 DEG C.At T=15 minute, sampling is used for gas-chromatography Analysis is to check that monomer converts.When monomer conversion is identified (about 30 minutes, T=45), reactor mixture is maintained at 100 DEG C At a temperature of 105 DEG C, until butyl acrylate > 80% of conversion.At the conversion, the reagent of active nitrogen cleaning into Material mixture was added into reactor during 180 minutes.During reagent feeds, the temperature of reaction is maintained at 100-105 Between DEG C.After completing reagent feeds, conversion of the reaction condition until realizing the butyl acrylate greater than 98% is maintained.Gained Polymer is subsequently cooled to environment temperature and is discharged from reactor.The total theoretical Mn of polymer is 50,000g/mol.Each Non-reacted section is 45,000g/mol and function end segments are 5,000g/mol.

The molecular weight (Mn) of total acrylate copolymer of measurement is 53,591g/mol (by relative to polystyrene mark Quasi- gel permeation chromatography measurement) and polydispersity be 1.51.So the Mw calculated is 80,922.

Embodiment 7: the random function distributed embodiments with alcohol functionalities

Following preparation has at random positioned at the acrylic copolymer of the active functionality of entire polymer chain, following usually aobvious It is shown as (29):

In the 1500ml reactor feed for being equipped with heating mantle, blender, reflux condenser, head tank and nitrogen inlet The toluene of 139.37g.Monomer is added into feed containers with following amounts:

83.16g 2-EHA；

239.51g ethoxy ethoxy ethyl acrylate；With

The acrylic 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

Initiator mixture in toluene, feed containers and monomer in reactor are bubbled with constant nitrogen at room temperature Cleaning 30 minutes.After the holding, the toluene in reactor is heated to 105 DEG C, reverses flow out condenser on a small quantity wherein having. In the point, monomer and initiator mixture were fed to reactor in 90 minutes.During reagent and initiator feed, reaction Device mixture is maintained under reflux at a temperature of between 105 DEG C and 116 DEG C.After reagent and initiator feed are completed, dimension Hold reaction condition 60 minutes.During 60 minutes keep, detonation (cook-off) catalyst charge is prepared in feed containers.It is quick-fried Combustion catalyst charge is made of the toluene of 24.28g and peroxidating neopentanoic acid spy's pentyl ester of 0.37g.Detonation catalyst is constant Nitrogen cleaning is lower to be bubbled 15 minutes.After 60 minutes keep, detonation catalyst was fed to reactor in 30 minutes.Once Detonation catalyst charge is depleted, and > 110 DEG C of reaction is maintained to continue 60 minutes.Resulting solution polymer is then cooled to ring Border temperature and from reactor be discharged.

The molecular weight (Mn) of total acrylate copolymer of measurement is 13,301g/mol (by relative to polystyrene mark Quasi- gel permeation chromatography measurement) and polydispersity be 2.76.So the Mw calculated is 36,711.

Embodiment 8-39

Embodiment 8-33 passes through UV exposure based on the acrylate copolymer mixed with reactive diluent and structural constituent Triggering passes through and is heating and curing to abundant intensity (structure) to convert solid PSA from liquid for adhesive.

Embodiment 8-33 is illustrated in table 7.

Table 7: the embodiment 8-33 of Adhesive composition

In table 7, IR refers to anti-impact force, is measured according to ASTM-G14-04 (2010).Rolling Ball Tack is according to ASTM- D3121-06 measurement.

Embodiment 34-36 illustrates the lap shear and Rolling Ball Tack measurement of the other Adhesive composition of this theme.

Embodiment 34 is the acrylate copolymer mixed with structural constituent, and dry through mild heat is PSA, and so It is fully cured by higher heat triggering afterwards to generate the structure between two substrates and combine.

Embodiment 35 is the acrylate copolymer mixed with both reactive oligomers and structural constituent, and is added through mild Heated drying is PSA, and is then fully cured by higher heat triggering to generate the structure between two substrates and combine.

Embodiment 36 is the acrylate copolymer mixed with reactive diluent and structural constituent, is touched by low-heat exposure Hair passes through higher heat cure to abundant intensity (structural) to convert PSA from liquid for adhesive.

Embodiment 34:AS-2549 acrylic acid PSA and AAA is crosslinked, and is mixed with Synasia S-21 epoxy resin, and And dry 10min leniently at 90 DEG C with solvent-free PSA film of casting.The initiator of heat cure for epoxy resin exists mostly Less than 95 DEG C of sluggish temperature.After desciccator diaphragm is to generate PSA adhesive tape, it is to be bonded given to it is expected that the adhesive tape can be applied Substrate.Upon application of the adhesive tape, applies other heat and converted with causing adhesive to abundant intensity.Structure is incorporated in 140 DEG C Lower formation continues 15 minutes.The description of the lap shear test of embodiment 34 is shown in Fig. 3.The program is as follows:

The lap shear data (Al and Al) of embodiment 34 are presented in table 8.

Table 8: lap shear data

Following measurement lap shear.ASTM D-1002 standard method of test is used for the single overlap joint by tensile load Connect the apparent shear strength (metal and metal) (reference) of viscous binding metal sample.Adhesive thickness is 0.0024 inch +/- 0.0006 inch.Load is 1 inch/minute.Measure peak load.

Embodiment 35:AS-2549 acrylic acid PSA and AAA are crosslinked, and with Synasia S-21 epoxy resin and KH4-67 Mixing, and dry 10min leniently at 90 DEG C with solvent-free PSA film of casting.The initiation of heat cure for epoxy resin Agent is sluggish mostly in the temperature less than 95 DEG C.After desciccator diaphragm is to generate PSA adhesive tape, the adhesive tape can be applied to expectation Substrate to be bonded.Upon application of the adhesive tape, applies other heat and converted with causing adhesive to abundant intensity.Structure knot Conjunction is formed at 140 DEG C, continues 15 minutes.Fig. 4 depicts the program that lap shear is tested 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 and 828 epoxy resin of EPON, TMPO and Siloquest A-187 Mixing.It solidifies 7min leniently at 110 DEG C with PSA film of casting.The initiator of heat cure for epoxy resin is being less than At a temperature of 110 DEG C very slowly.After desciccator diaphragm is to generate PSA adhesive tape, the adhesive tape can be applied to it is expected base to be bonded Plate.Upon application of the adhesive tape, applies other heat and converted with causing adhesive to abundant intensity.Structure is incorporated at 140 DEG C It is formed, continues 15 minutes.

The lap shear data (Al and Al) of embodiment 36 are presented in table 10.

Table 10: the Rolling Ball Tack data of embodiment 36

Embodiment 37: substrate and then suitably solid by being exposed to actinic radiation is applied to according to the liquid of this theme Change.Diagram is described in Fig. 5.Specifically, Fig. 5 schematically depict apply liquid or other compositions to film, label and/ Or on container, and it is exposed to actinic radiation, to suitably solidify liquid or composition.Provide has as described herein Region, the film in face or surface or the source of label 10 that liquid or composition 20 are coated with.In some embodiments, it is possible to provide glutinous Adhesive one or more regions 25 or band 30 to help primitively to fix film or label to interested container 40. Before, during and/or after suitable application film or label to container, actinic radiation 50 is led into coating, thus adherency and/ Or solidify coating, and generate the container 45 of label.This is usually expressed as operation A in Fig. 5.Initially apply film or label it Afterwards, the removing and/or application of heat can be carried out.It can be carried out before, during and/or after operation (one or more) A other Operation.Fig. 5 also diagrammatically illustrates the continuous process 100 that plurality of container 140 receives film or label, in closure member 150 It is exposed to actinic radiation inside to generate the container 145 of multiple labels.

Following table 11 includes representing the exemplary formulation of the embodiment of this theme.Said preparation includes the thickening illustrated as follows Component, free radical addition diluent, structure diluent and photoinitiator and additive are (i.e.1010)。

Table 11: the illustrative embodiments of Adhesive composition

Following table 12 shows the performance data of the selection of certain preparations in table 11.

Table 12: the performance data of the selection of preparation in table 11

Embodiment 38: two kinds of other Adhesive compositions according to this theme are illustrated in following table 13 and 14.

Table 13: Adhesive composition EXP-MW2-070-A

Table 14: Adhesive composition EXP-MW2-070-B

Embodiment 39: several other compositions according to this theme are illustrated in following table 15 and 16.These combinations The concrete application of object is " roll tightly, tighten " (ROSO) label or the relevant technologies.

Table 15: it rolls tightly, tighten composition

Table 16: it rolls tightly, tighten composition

It applies and develops from the future of the technology, many other benefits will undoubtedly become apparent.

The application of all patents, publication that are mentioned above and article are incorporated into here by reference with their entirety.

This theme includes the combination of the component and aspect of various compositions as described herein.Thus, for example, this theme includes The one or more components and/or feature of a kind of embodiment and other embodiments (one or more) it is one or more its His component and/or feature combine.

As herein above described, this theme is solved asks to strategy, system and/or the relevant many of equipment before Topic.It should be understood, however, that those skilled in the art can to be described herein and illustrating with explain this theme essence it is thin The arrangement of section, material and component carries out various changes, without departing from the principle and range of claimed theme, such as appended right It is expressed in it is required that.

Claims (8)

1. a kind of appropriate cured pressure-sensitive adhesive agent comprising:

The acrylic acid base polymer of the Mw with 100,000 to 1,000,000 of 20-80wt%；

The tackifier of 0-30wt%；

At least one liquid reactions oligomer of 5-40wt%；

The epoxy functionalized component of at least one acrylic acid-of 0-30wt%；

The epoxy functionalized alkene of 0-30wt%；

Metal chelate crosslinMng agent-catalyst of 0-2wt% and at least one of external catalyst；With

One or more structure diluents of 5-40wt%, wherein the structure diluent is selected from: S-21, S-28, Epon 828, Epon 834、A-186、A-187、EP-10、Desmolux D100、Desmolux D200、Desmodur N3200、 Desmodur N100, Desmodur N3300, the PPO oligomer less than 5,000 dalton, TMPO, less than 5,000 dalton PEO oligomer, 2EH oxetanes, bifunctional oxetanes, following formula (7) Ethoxylated bisphenol A diacrylate Ester --- wherein n+m=3, the ethoxylated trimethylolpropane triacrylate of following formula (8), following formula (9) bisphenol-A two Diglycidyl ether diacrylate, 1,2- cyclic ethers, 1,3- cyclic ethers, 1,4- cyclic ethers, acid anhydride, lactone, lactams, cyclic ethers, siloxanes, Oxazoline,Oxazolidine and bismaleimide；

The pressure-sensitive adhesive agent and the reactive oligomers are configured to be exposed to stimulation post-crosslinking.

2. adhesive according to claim 1, wherein the acrylic plinth polymer has 250,000 to 750,000 Mw.

3. adhesive according to claim 1, wherein the stimulation is selected from: radiation, heat, moisture, pressure, ultrasound, chemistry Exposed and a combination thereof.

4. adhesive according to claim 1, wherein the crosslinking is condensation cross-linking.

5. adhesive according to claim 1, wherein the structure diluent is selected from: S-21, S-28, Epon 828, Epon 834、A-186、A-187、EP-10、Desmolux D100、Desmolux D200、Desmodur N3200、 Desmodur N100, Desmodur N3300, the PPO oligomer less than 5,000 dalton, TMPO, less than 5,000 dalton PEO oligomer, 2EH oxetanes, bifunctional oxetanes, following formula (7) Ethoxylated bisphenol A diacrylate Ester --- wherein n+m=3, the ethoxylated trimethylolpropane triacrylate of following formula (8), following formula (9) bisphenol-A two Diglycidyl ether diacrylate, 1,2- cyclic ethers, 1,3- cyclic ethers, 1,4- cyclic ethers, butyrolactone, valerolactone, caprolactone, methyl-fourth Lactone, butyrolactam, valerolactam, caprolactam, cyclic ethers, siloxanes,Oxazoline,Oxazolidine, bismaleimide,

6. a kind of appropriate cured pressure-sensitive adhesive agent comprising:

The acrylic acid base polymer of the molecular weight with 100,000 to 1,000,000 of 20-80wt%；

The tackifier of 0-30wt%；

At least one liquid reactions oligomer of 5-40wt%, at least one liquid reactions oligomer is Silante terminated Polyethers；

The epoxy functionalized component of at least one acrylic acid-of 0-30wt%；

The epoxy functionalized alkene of 0-30wt%；

Metal chelate crosslinMng agent-catalyst of 0-2wt% and at least one of external catalyst.

7. adhesive according to claim 6 further comprises one or more structure diluents of 5-40wt%.

8. adhesive according to claim 7, wherein the structure diluent is selected from: S-21, S-28, Epon 828, Epon 834、A-186、A-187、EP-10、Desmolux D100、Desmolux D200、Desmodur N3200、 Desmodur N100, Desmodur N3300, PPO oligomer, trihydroxy methyl with the molecular weight less than 5,000 dalton Propane oxetanes, the PEO oligomer with the molecular weight less than 5,000 dalton, 2EH oxetanes, bifunctional oxygen Azetidine, the trimethylolpropane trimethacrylate of following formula (5), following formula (6) tri (propylene glycol) diacrylate, The ethoxylated bisphenol a diacrylate of following formula (7) --- wherein n+m=3, following formula (8) ethoxylation trihydroxy methyl Propane triacrylate, the bisphenol A diglycidyl ether diacrylate of following formula (9), 1,2- cyclic ethers, 1,3- cyclic ethers, 1,4- Cyclic ethers, acid anhydride, lactone, lactams, cyclic ethers, siloxanes,Oxazoline,Oxazolidine and bismaleimide；