CN105051134A - Adhesives and related methods - Google Patents

Abstract

A cure-in-place pressure sensitive adhesive composition is described that includes one or more bodying components, structural diluents, free radical diluents, and additives such as crosslinkers, external catalysts, photoinitiators, and stabilizers/processing aids. The bodying component may be acrylic or non-acrylic.

Description

Adhesives and related methods

Cross References to Related Applications

This application claims priority to US Provisional Application Serial No. 61/711,386, filed October 9, 2012.

technical field

The subject matter generally relates to reactive oligomers and/or compounds blended with acrylate or vinyl-acrylate base polymers. In some forms, non-acrylate polymers are used in the blend. The blend results in a pressure sensitive adhesive (PSA) comprising latent functionality on the oligomer and/or additives for proper crosslinking. Crosslinking can be triggered by surface catalysis, UV irradiation or other curing mechanisms.

In particular, the present subject matter relates to pressure sensitive adhesive compositions, and more particularly to pressure sensitive adhesives having high adhesion over a broad temperature range. This subject also relates to proper curing of liquid compositions. The subject matter also relates to methods of forming and methods of using such compositions. The subject matter further relates to foam articles incorporating the composition.

Contents of the invention

This subject matter generally relates to pressure sensitive adhesives that are properly cured by UV light, surface catalysis, or some other mechanism, and that achieve much higher strength than typical PSAs. The adhesive is typically formed by blending a reactive oligomer with one or more high molecular weight acrylate polymers. An example is a blend of a silane functional acrylic polymer and a silyl terminated polyether. The blend is inherently tacky and can be cured by exposing the blend to a compound comprising an oligomeric silane, such as can be printed on a mating surface.

In one embodiment, the subject pressure sensitive adhesive or suitably cured composition is formed from a blend comprising (a) a reactive oligomer and (b) a high molecular weight acrylate polymer. The blend is inherently tacky and is cured by exposing the blend to a compound comprising an oligomeric silane that can be introduced on the surface by printing.

Another embodiment of the present subject matter is a suitably cured pressure sensitive adhesive comprising: (a) 20-80 weight percent (wt %) of a bodying component comprising 5,000 to 1,000,000, at an acrylic base polymer of molecular weight (Mw) of 15,000-250,000 in certain embodiments, and 15,000-100,000 in still other embodiments, (b) 5-50 wt% of one or more structural diluents, ( c) 10-80 wt% of one or more free radical addition diluents, (d) 0-4.0 wt% of one or more crosslinking agents, (e) 0-4.0 wt% of one or more an external catalyst, (f) 0.01-10 wt% of one or more photoinitiators, and (g) 0-10.0 wt% of one or more stabilizers/processing aids.

Yet another embodiment of the present subject matter is a suitably cured pressure sensitive adhesive comprising (a) 20-80 wt. 100,000, and in still other embodiments 1000-50,000 Mw of a base polymer selected from the group consisting of polyolefins, polyvinylaromatics, polyurethanes, polycarbonates, polyesters, polyethers, and combinations thereof , (b) 5-50wt% of one or more structural diluents, (c) 10-80wt% of one or more free radical addition diluents, (d) 0-1.0wt% of one or more A plurality of crosslinking agents, (e) 0-4.0wt% of one or more external catalysts, (f) 0.01-10wt% of one or more photoinitiators, and (g) 0-10.0wt% of One or more stabilizers/processing aids.

Additional embodiments of the subject matter include suitably cured pressure sensitive adhesives comprising: (a) 20-80 wt% of an acrylic base polymer having a Mw of 100,000 to 1,000,000 and in certain embodiments 250,000-750,000 , (b) 0-30 wt% of one or more tackifiers, (c) 5-40 wt% of one or more liquid reactive components, (d) 0-30 wt% of acrylic-epoxy functional component and/or epoxy functional olefin, and (e) 0-2 wt% metal chelate crosslinker-catalyst and/or external catalyst.

Additional embodiments of the subject matter include suitably cured pressure sensitive adhesives comprising: (a) 50-80 wt% of an acrylic base polymer having a Mw of 250,000-750,000, (b) 10-30 wt% of a or more structural diluents, (c) 0-0.5wt% metal chelate crosslinker, (d) 0-2wt% one or more external catalysts, and (e) 0-10wt% stabilizer agent/processing aid.

Additional embodiments of the present subject matter include suitably cured pressure sensitive adhesives comprising: (a) 50-80 wt% of an acrylic base polymer having a Mw of 250,000-750,000, (b) 20-40 wt% of a or structural diluents, (c) 0-30 wt% optional acrylic-epoxy functional component, (d) 0-0.5 wt% metal chelate crosslinker, (e) 0-2 wt% One or more external catalysts, and (f) 0-10 wt% stabilizers/processing aids.

Additional embodiments of the present subject matter include suitably solidified liquids comprising: (a) 5-70% by weight of a thickening component comprising from 5,000 to 1,000,000, in certain embodiments Acrylic base polymer of Mw of 15,000-100,000 in other embodiments, (b) 5-40 wt% of one or more structural diluents, (c) 30-95 wt% of one or more free radical addition Diluent, (d) 0-10.0wt% of one or more external catalysts, (e) 0-10wt% of one or more photoinitiators, (f) 0-10wt% of one or more Photosensitizer, and (g) 0-10 wt% stabilizer(s).

Additional embodiments of the subject matter include suitably cured liquids comprising: (a) 5-50 wt% of a thickening component comprising an acrylic base polymer having a Mw of 15,000 to 100,000, (b) 50-95 wt% One or more structural diluents, (c) 0.01-10 wt% of one or more external catalysts, and (d) 0-10 wt% of stabilizers/processing aids.

Additional embodiments of the subject matter include suitably cured liquids comprising (a) 30-70 wt% of a thickening component comprising an acrylic copolymer having a Mw of 15,000-100,000, (b) 7-70 wt% of a One or more structural diluents, (c) one or more free radical addition diluents of 7-70wt%, (d) one or more photoinitiators of 2-10wt%, (e) 0- 1% of one or more antioxidants, and (f) 0-10 wt% stabilizers/processing aids.

Additional embodiments of the present subject matter include suitably solidified liquids comprising: (a) 5-70% by weight of a thickening component comprising from 5,000 to 1,000,000, in certain embodiments Acrylic base polymer of Mw of 15,000-100,000 in other embodiments, (b) 5-80 wt% of one or more structural diluents, (c) 5-70 wt% of one or more free radical addition Diluent, (d) 0-5.0wt% of one or more external catalysts, (e) 0-10wt% of one or more photoinitiators, (f) 0-10wt% of one or more photosensitizer, and (g) 0-10 wt% stabilizer/processing aid.

Additional embodiments of the present subject matter include suitably cured liquids comprising: (a) 10-15 wt% of a thickening component comprising an acrylic base polymer having a Mw of 15,000-100,000, (b) 45-60 wt% One or more structural diluents of (c) 30-40wt% of one or more free radical addition diluents, (d) one or more external catalysts of 0.01-2.0wt%, (e) 0.01-10 wt% photoinitiator, (f) 0-10 wt% one or more photosensitizers, and (g) 0-10 wt% stabilizer/processing aid.

Additional embodiments of the present subject matter include suitably solidified liquids comprising: (a) 5-70% by weight of a thickening component comprising from 1,000 to 500,000, in certain embodiments In other embodiments is a non-acrylic base polymer of 1,000-50,000 Mw selected from the group consisting of polyolefins, polyvinylaromatics, polyurethanes, polycarbonates, polyesters, polyethers, and combinations thereof, (b) 5-80wt% of one or more structural diluents, (c) 0-40wt% of one or more free radical addition diluents, (d) 0-5.0wt% of one or more An external catalyst, (e) 0-10wt% of one or more photoinitiators, (f) 0-10wt% of one or more photosensitizers, and (g) 0-10wt% stabilizer/processing Auxiliary.

Additional embodiments of the present subject matter include suitably cured liquids comprising: (a) 5-50 wt% of a thickening component comprising non-acrylic acid having a Mw of 5,000 to 1,000,000 and in certain embodiments 15,000-100,000 polymer, (b) 50-95 wt% of one or more structural diluents, (c) 0.01-10 wt% of one or more external catalysts, and (d) 0-10 wt% of stabilizers/processing aids agent. The non-acrylic polymer is selected from polyolefins, polyvinylarenes, polyurethanes, polycarbonates, polyesters, polyethers, and combinations thereof.

Additional embodiments of the present subject matter include suitably solidified liquids comprising: (a) 5-70% by weight of a thickening component comprising from 1,000 to 500,000, in certain embodiments In other embodiments is a non-acrylic base polymer of 1,000-50,000 Mw selected from the group consisting of polyolefins, polyvinylaromatics, polyurethanes, polycarbonates, polyesters, polyethers, and combinations thereof, (b) 5-80wt% of one or more structural diluents, (c) 5-70wt% of one or more free radical addition diluents, (d) 0-5.0wt% of one or more An external catalyst, (e) 0-10wt% of one or more photoinitiators, (f) 0-10wt% of one or more photosensitizers, and (g) 0-10wt% stabilizer/processing Auxiliary.

Additional embodiments of the present subject matter include suitably solidified liquids comprising: (a) 10-15% by weight of a thickening component comprising from 1,000 to 500,000, in certain embodiments 1,000-100,000, and in still Non-acrylic polymers of Mw of 1,000-50,000 in other embodiments, (b) 45-60 wt% of one or more structural diluents, (c) 30-40 wt% of one or more free radical addition Diluent, (d) 0.01-2.0wt% of one or more external catalysts, (e) 0.01-10wt% of one or more photoinitiators, (f) 0-10wt% of one or more photosensitizer, and (g) 0-10 wt% stabilizer/processing aid. The non-acrylic polymer is selected from polyolefins, polyvinylarenes, polyurethanes, polycarbonates, polyesters, polyethers, and combinations thereof.

Additional embodiments of the present subject matter include suitably solidified liquids comprising: (a) 5-70% by weight of a thickening component comprising from 5,000 to 1,000,000, in certain embodiments an acrylic base polymer having a Mw of 15,000-100,000 in other embodiments, (b) 5-70% by weight of a thickening component comprising 1,000-500,000, in certain embodiments 1,000-100,000, and in still In other embodiments is a non-acrylic base polymer of 1,000-50,000 Mw selected from the group consisting of polyolefins, polyvinylaromatics, polyurethanes, polycarbonates, polyesters, polyethers, and combinations thereof, (c) 5-80wt% of one or more structural diluents, (d) 0-40wt% of one or more free radical addition diluents, (e) 0-5.0wt% of one or more An external catalyst, (f) 0-10wt% of one or more photoinitiators, (g) 0-10wt% of one or more photosensitizers, and (h) 0-10wt% stabilizer/processing Auxiliary.

Additional embodiments of the present subject matter include suitably solidified liquids comprising: (a) 5-50% by weight of a thickening component comprising from 5,000 to 1,000,000, and in some In other embodiments an acrylic base polymer with a Mw of 15,000-100,000, (b) 5-50% by weight of a thickening component comprising non- Acrylic base polymer, said non-acrylic base polymer is selected from polyolefin, polyvinyl aromatic hydrocarbon, polyurethane, polycarbonate, polyester, polyether and its combination, (c) 50-95wt% one or more A structural diluent, (d) 0.01-10 wt% of one or more external catalysts, (e) 0-10 wt% of one or more photosensitizers, and (f) 0-10 wt% of stabilizer/processing Auxiliary.

Additional embodiments of the present subject matter include suitably solidified liquids comprising: (a) 70-80 weight percent of a thickening component comprising Acrylic copolymer, (b) 15-20 wt% of one or more structural diluents, (c) 0.01-5 wt% of one or more photoinitiators, and (d) 0-10 wt% of stabilizer/ Processing aids.

Additional embodiments of the present subject matter include suitably solidified liquids comprising: (a) 5-15% by weight of a thickening component comprising from 5,000 to 1,000,000, and in some an acrylic base polymer having a Mw of 15,000-100,000 in other embodiments, (b) 5-15 wt. In other embodiments is a non-acrylic base polymer of 1,000-50,000 Mw selected from the group consisting of polyolefins, polyvinylaromatics, polyurethanes, polycarbonates, polyesters, polyethers, and combinations thereof, (c) 45-60wt% of one or more structural diluents, (d) 30-40wt% of one or more free radical addition diluents, (e) 0.01-2.0wt% of one or more An external catalyst, (f) 0.01-10wt% of one or more photoinitiators, (g) 0-10wt% of one or more photosensitizers, and (h) 0-10wt% stabilizer/processing Auxiliary.

Additional embodiments of the subject matter include suitably solidified liquids. The liquid comprises (a) 5-70% by weight of a thickening component comprising a non-acrylic base polymer having a Mw of 5,000 to 1,000,000 selected from the group consisting of polyolefins, polyvinylaromatics, polyurethanes , polycarbonate, polyester, polyether and combinations thereof; (b) 0-40 wt% of at least one structural diluent; (c) 30-95 wt% of at least one free radical addition diluent; (d) 0-10.0 wt% curing agent; (e) 0-10 wt% photosensitizer; and (f) 0-10 wt% stabilizer.

Another embodiment of the present subject matter includes a method of curing a pressure sensitive adhesive. Specifically, a method of curing a pressure sensitive adhesive comprises providing a suitably cured pressure sensitive adhesive comprising 20-80% by weight of a thickening component comprising Acrylic base polymer, 5-50 wt% of at least one structural diluent, 10-80 wt% of at least one free radical addition diluent, 0-10.0 wt% of crosslinking agent, 0-4.0 wt% of the first Curing agent, 0.01-10 wt% secondary curing agent, and 0-10.0 wt% stabilizer/processing aid. The method also includes exposing or subjecting the adhesive to a first stimulus selected from radiation, heat, moisture, pressure, ultrasound, chemical exposure, and combinations thereof.

Another embodiment of the present subject matter includes a suitably cured pressure sensitive adhesive comprising (a) 50-80 wt% of an acrylic base polymer having a Mw of 250,000-750,000; (b) 10-30 wt% of at least one A structural diluent; (c) 0-0.5 wt% of at least one metal chelate crosslinker; (d) 0-2 wt% curing agent; and (e) 0.1-10 wt% stabilizer/processing aid agent.

As will be realized, the subject matter described herein is capable of other and different embodiments, and its several details are capable of modifications in various respects, all without departing from claimed subject matter. Accordingly, the drawings and description are to be regarded as illustrative and not restrictive.

Description of drawings

FIG. 1 depicts a dynamic mechanical analysis of certain embodiments of the properly cured pressure sensitive adhesive of Example 3. FIG.

Figure 2 depicts the general bonding method of the subject matter.

FIG. 3 depicts the procedure for the Lap Shear Test (LapShearTest) of Example 34. FIG.

Figure 4 depicts the procedure for the lap shear test of Example 35.

Figure 5 depicts a schematic of the application of a liquid to a substrate and the subsequent proper curing of the liquid by exposure to actinic radiation.

Figure 6 is a schematic flow diagram depicting a bonding method according to the present subject matter.

Detailed description of the invention

In certain embodiments, the subject suitably cured adhesives include (i) a thickening component, which may be acrylic-based or non-acrylic-based or include a combination of acrylates and non-acrylates, (ii) One or more structural diluents, (iii) one or more free radical addition diluents, and (iv) one or more additives, such as (a) crosslinkers, (b) catalysts such as thermal catalysts and base catalysts, (c) photoinitiators, which include free radical photoinitiators, UV free radical photoinitiators, and type I and II photoinitiators, (d) photosensitizers including dyes, and (e) stabilizers or Processing aids. An overview of the selection of the three main components (i)-(iii) can be seen in Table 1 below.

Table 1: Representative List of Major Components of Compositions

Details of these various components are provided herein.

thickening component

A thickening component is broadly defined herein as having a molecular weight (Mw) of at least 25,000 Daltons. The thickening component(s) may be present at 10-90 wt%, in some embodiments 20-80 wt%, and in still other embodiments 30-70 wt%, alternatively 5-70 wt% , optionally 40-60 wt%, alternatively 30-50 wt%, alternatively 5-15 wt%, alternatively 10-15 wt%, or 80 wt% is present in the subject composition. The thickening component may be an acrylic based thickening component or a non-acrylic based thickening component. Combinations of these and potentially other components can be used. The thickening component may have 5,000 to 1,000,000, in some embodiments 15,000-250,000, and in still other embodiments 15,000-100,000, alternatively 1,000 to 500,000, in some forms 1,000-100,000, and a molecular weight (Mw) of 1,000-50,000, or alternatively 18,000-70,000 in still other forms.

In certain embodiments of the subject matter, specific acrylic-based thickening components may be used as follows. It should be understood that the present subject matter includes the use of the corresponding methacrylate monomer, oligomer or component in place of any indicated acrylate monomer, oligomer or component, or in addition to them.

MJZ4-87-1: Thickening component. The ^thickening component has a number average molecular weight (Mn ) (polydispersity index (PDI) 3.5, random copolymer) random acrylic copolymer.

MW1-65: Thickening component. The thickening component is composed of 50 wt% 2-ethylhexyl acrylate, 48 wt% methyl acrylate and 2 wt% Additol ^™ S-100 with a Mn of 50k (PDI3.5, random copolymer) Random acrylic copolymer.

MW1-69: Thickening component. The thickening component is composed of 44.9wt% 2-ethylhexyl acrylate, 43.1wt% methyl acrylate 43.1%, 10.2wt% Elvacite ^™ 1020 (pMMA) and 1.8wt% Additol ^™ S-100 A random acrylic copolymer with a Mn of 50k (PDI3.5, random copolymer).

MW1-91: Thickening component. The thickening component is composed of 56.1 wt% 2-ethylhexyl acrylate, 25.5 wt% vinyl acetate, 18.4 wt% methyl acrylate with a Mn of 50k (PDI3.5, random copolymer) random acrylic copolymers.

MW1-93 (the best synthetic example is MW1-101). This thickening component is to have the Mn(PDI3. 5, random copolymer) random acrylic copolymer.

MW1-94: Thickening component. The thickening component is an adduct of acrylic acid and MW 1-93 comprising 98 wt% MW 1-93 and 2 wt% glycidyl methacrylate and a chromium (3+) catalyst.

The detailed formulations of some of the thickening components presented in Table 1 are illustrated in Table 2 below.

Abbreviations in the aforementioned Table 2 include: BA: butyl acrylate; 2-EHA: 2-ethylhexyl acrylate; tBA: tert-butyl acrylate; EOEOEA: ethoxyethoxyethyl acrylate; Propylene Oxide, BMA: Butyl Methacrylate.

free radical addition diluent

Free radical addition diluents are acrylic-based monomers having a molecular weight (Mw) generally less than 25,000 and/or generally having a viscosity below 25,000 cps at 25°C. Free radical addition diluents are sometimes referred to herein as reactive diluents. The free radical addition diluent is 10-80wt%, in some embodiments is 50-70wt%, alternatively 10-60wt%, alternatively 5-70wt%, alternatively 0-40wt%, in still In other embodiments an amount of 30-40 wt%, or alternatively 7-25 wt% is present in the subject composition. Free radical addition diluents may include (meth)acrylate monomers and in some forms have an overall Mw of less than 10,000 Daltons. Examples of free radical addition diluents useful herein include ACE, isostearyl acrylate, heptadecyl acrylate, dicyclopentadienyl acrylate, THF acrylate, alkoxylated THF acrylate, hydroxyacrylate Ethyl ester, phenoxyethyl acrylate, urethane acrylate (Mw<2000), OXE-10, OXE-30, S-100, V2100, cycloaliphatic V2100 and PAMA. Many of these components are described in more detail herein with examples. Several examples of free radical addition diluents are detailed below.

Alkoxylated THF acrylate is a low viscosity monofunctional monomer available from Sartomer as CD-611, where n is not disclosed, and which is shown below as formula (1):

Hydroxyethyl Acrylate: This free radical addition diluent is shown below as formula (2):

Phenoxyethyl Acrylate: This free radical addition diluent is shown below as formula (3):

This low viscosity monofunctional monomer is available from Sartomer as SR339.

Tetrahydrofuryl Acrylate (THFA or THF Acrylate): This free radical addition diluent is shown below as formula (4). This low viscosity monofunctional monomer is available from Sartomer as SR285.

Structural diluents may be present in the subject compositions in amounts of 5-80 wt%, alternatively 5-50 wt%, in certain embodiments 10-50 wt%, alternatively 5-40 wt%, Optionally 10-30wt%, Optionally 20-40wt%, Optionally 65-95wt%, Optionally 75-85wt%, Optionally 75-95wt%, Optionally 7-25wt%, Optionally Preferably 45-65 wt%, alternatively 45-60 wt%, alternatively 75-85 wt% and alternatively 15-20 wt%. Structural diluents are sometimes referred to herein as structural components. Various structural diluents and details are described in connection with the examples herein.

Various structural diluents include the following: Trimethylolpropane triacrylate (TMPTA). This monomer is available from Sartomer as SR351 and is shown as formula (5) as follows:

Tripropylene glycol diacrylate, available from Sartomer as SR306, and shown below as formula (6):

Ethoxylated (3 mol) bisphenol A diacrylate. This monomer is available from Sartomer as SR349, where n+m=3, and is shown in formula (7) as follows:

Ethoxylated (3 mol) trimethylolpropane triacrylate, and shown as formula (8) as follows:

This monomer is available from Sartomer as SR454.

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

This monomer is available from Cytec as Ebecryl600.

The radical structural component includes one or more curable materials, including homopolymers having a Tg > 0°C. Such suitable components include trimethylolpropane triacrylate (TMPTA), ethoxylated (xmol) bisphenol A diacrylate, ethoxylated (xmol) trimethylolpropane triacrylate and bis Phenol A diglycidyl ether diacrylate. The value x is from 1 to 10, in certain embodiments from 1 to 5, and in still other embodiments is 3.

Ring-opened structural components may also be used in certain embodiments. Suitable ring-opening structure components include S-21, S-28, Epon828, Epon834, A-186 and A-187. Also useful are epoxies, oxetanes, anhydrides and lactams.

Cationic polymerizable monomers include epoxy-containing materials, alkyl vinyl ethers, cyclic ethers, styrene, divinylbenzene, vinyltoluene, N-vinyl compounds, 1-alkyl olefins (α-olefins) , lactams and cyclic acetals.

Epoxy-containing materials curable or polymerizable by the subject catalytic system are those known to undergo cationic polymerization, and include 1,2-cyclic ethers, 1,3-cyclic ethers, and 1,4-cyclic ethers (also named are 1,2-epoxides, 1,3-epoxides and 1,4-epoxides). 1,2-Cyclic ethers are used in some forms of the subject matter.

Cyclic ethers polymerizable in accordance with this subject matter include those described in Frisch and Reegan, Ring-Opening Polymerizations, Vol. 2 (1969). Suitable 1,2-cyclic ethers are monomeric and polymeric epoxides. They may be aliphatic, cycloaliphatic, aromatic or heterocyclic and will generally have an epoxy equivalent weight of from 1 to 6 and in certain embodiments 1 to 3. Especially useful are aliphatic, cycloaliphatic and glycidyl ether type 1,2-epoxides such as propylene oxide, epichlorohydrin, styrene oxide, vinylcyclohexene oxide, vinylcyclohexene di Ketone, glycidol, butadiene oxide, glycidyl ether of bisphenol A, cyclohexene oxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3, 4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexylcarboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl) Adipic acid, dicyclopentadiene dioxide, epoxidized polybutadiene, 1,4-butanediol diglycidyl ether, polyglycidyl ether of phenol-formaldehyde resole or novolak resin, isophthalic acid Phenol diglycidyl ethers and epoxy siloxanes, eg dimethyl siloxanes with cycloaliphatic epoxide or glycidyl ether groups.

Various commercial epoxy resins are available and listed in Lee and Neville, Handbook of Epoxy Resins, (1967) and in P. Bruins, Epoxy Resin Technology, (1968). Representative 1,3- and 1,4-cyclic ethers polymerizable according to this subject matter are oxetane, 3,3-bis(chloromethyl)oxetane and tetrahydrofuran.

In particular, readily available cyclic ethers include propylene oxide, oxetane, epichlorohydrin, tetrahydrofuran, styrene oxide, cyclohexene oxide, vinyl cyclohexene oxide, glycidol, octyl oxide, Phenyl glycidyl ether, 1,2-butylene oxide, glycidyl ether of bisphenol A (e.g., Epon828 and DER331), vinylcyclohexenedione (e.g., ERL-4206), 3,4-epoxy Cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (for example, ERL-4221), 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6- Methylcyclohexanecarboxylate (eg, ERL-4201), bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate (eg, ERL-4299), polypropylene glycol-modified fat epoxy resins (e.g., ERL-4050 and ERL-4052), dipentene dioxide (e.g., ERL-4269), epoxidized polybutadiene (e.g., Oxiron 2001), silicone epoxy resins (e.g., , Syl-Kem90), 1,4-butanediol diglycidyl ether (e.g., AralditeRD-2), polyglycidyl ethers of formaldehyde novolac resins (e.g., DER-431), Epi-Rez521 and DER-438) , resorcinol diglycidyl ether (e.g., Kopoxite), polyglycol diepoxide (e.g., DER-736), polyacrylate epoxide (e.g., EpocrylU-14), urethane modified (e.g., QX3599), multifunctional flexible epoxides (e.g., Flexibilizer 151), and mixtures thereof, and mixtures thereof with also well-known co-curing agents, curing agents, or hardeners (see Lee and Neville and Bruins). Typical hardener co-curing agents that can be used are acid anhydrides such as methylnadic anhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, and mixtures thereof .

Cationically polymerizable monomers useful in this subject matter include, but are not limited to, epoxy-containing materials, alkyl vinyl ethers, cyclic ethers, styrene, divinylbenzene, vinyltoluene, N-vinyl compounds, cyanic acid Esters, 1-alkenes (alpha olefins), lactams and cyclic acetals.

Additional cationically polymerizable monomers are described in US Patent No. 5,252,694 at column 4, line 30 to column 5, line 34. Specific monomers of this type include 828, and 1001F and the ERL series of cycloaliphatic epoxy monomers such as or Particularly useful monomers are the ERL series because of their lower cure temperatures.

Certain lactones can be used on this topic. Lactones useful as comonomers in the subject matter include those shown below as formulas (10)-(12):

wherein n is 4 or 5, h, i, k and m are independently 1 or 2, and each R is independently selected from H or a hydrocarbon group comprising up to 12 carbon atoms. Specific lactones are those wherein R is hydrogen or methyl, and particularly useful lactones in certain embodiments are e-caprolactone, d-valerolactone, glycolide (1,4-dioxo heterocyclohexane-2,5-dione), 1,5-dioxepan-2-one and 1,4-dioxepan-2-one.

Another type of diluent that can be used in the subject matter is the ring-opening monomeric diluent. This diluent is also non-reactive with other reactants under the conditions of free radical polymerization employed, and it is capable of undergoing ring opening after formation of the acrylate polymer during the curing step. Such ring-opening diluents include, but are not limited to, lactones, lactams, cyclic ethers, and cyclosiloxanes represented by the following general formulas shown below as (13)-(16):

In formulas (13)-(16), x ranges from, for example, 3 to 11, and in some forms 3-6 alkylene groups.

US Patent No. 5,082,922 describes ring-opening monomers as diluents for the solvent-free formation of polymers from ethylenically unsaturated monomers. However, this patent describes a single-step reaction of monomers together with a ring-opening diluent. This differs from the two-step strategy of certain methods of the subject matter, which provide for initial formation of the polymer from ethylenically unsaturated monomers, followed by curing of the diluent in the presence of the polymer thus formed. The mentioned patents provide for the use of reaction conditions, such as temperatures of at least 150°C, which support two reactions in a single step.

Useful ring-opening monomer diluents include, but are not limited to, butyrolactone, valerolactone, caprolactone, methyl-butyrolactone, butyrolactam, valerolactam, caprolactam, and silicones.

A siloxane ring-opening monomer is A-186, which acts as a ring-opening curing structural component as well as a silane-functional structural component through a silane-silane condensation reaction. A-186 (β(3,4-epoxycyclohexyl)ethyltrimethoxysilane) has the following formula (17):

Although the polymerization reaction can be carried out in the presence of a non-reactive solvent, the reaction advantageously occurs substantially solvent-free. In certain embodiments, the solvent will be present in an amount up to about 10 percent by weight, and preferably no greater than 5 percent by weight, based on the total weight of the reactants. Solvent can be removed (eg by heating) from the product of the diluent reaction step. Exemplary non-reactive solvents include ketones, alcohols, esters, and hydrocarbon solvents, such as ethyl acetate, toluene, and xylene.

for this topic oxazoline or The oxazolidines include those having the following formulas (18)-(19):

wherein R represents a branched, saturated aliphatic hydrocarbon group comprising 5 to 8 carbons. another suitable Azoline is shown below as (20):

wherein R represents a branched, saturated aliphatic hydrocarbon group comprising 5 to 8 carbons.

This article is useful The oxazolidine mixture typically has a viscosity of less than 8,000 mPa.s, and in some forms less than 6,500 mPa.s at 23° C., and is therefore suitable as a solvent-free hardener for polymer precursors containing isocyanate groups. In combination with polymer precursors comprising isocyanate groups, they are suitable for the production of solvent-free or low-solvent, one-component systems, which in turn are suitable as adhesives for high-quality paints, coating compositions or sealing compositions. These systems are usually cured after application by exposure to atmospheric humidity. Isocyanate group-containing polymer precursors suitable for the production of these systems include the organic polyisocyanates or isocyanate prepolymers described, for example, in US Patent No. 4,002,601. Generally, useful herein are described in U.S. Patent No. 5,189,176 oxazoline.

In certain embodiments, bismaleimides can be used. Bismaleimides useful in this subject matter are organic compounds containing two maleimide groups and are generally prepared from maleic anhydride and diamines. Bismaleimides can be described by the general formula (21) as follows:

where ^R3 is a divalent aromatic or alicyclic organic group. In certain forms, useful bismaleimides are derived from aromatic diamines, and especially those wherein ^R is a polynuclear aromatic group. Examples of such bismaleimides include 2,2-bis(4-aminophenoxy-4-phenyl)propane bismaleimide, 4,4'-bis(3-aminophenoxy ) diphenylsulfone bismaleimide, 1,4-bis(3-aminophenylisopropylidene)benzene bismaleimide and bis(4-aminophenyl)methane bismaleimide . The bismaleimides can be used alone or as a mixture.

It is also possible to use bismaleimides in which up to 50% of the maleimide groups are substituted maleimide groups such as methylmaleimide or halomaleimide amines or replaced by nadicimide, methylnadicimide or isomaleimide groups. Portions of the maleimide groups may also be replaced by succinimide, phthalimide or substituted succinimide and phthalimide groups.

Bismaleimides can be prepared from maleic anhydride and diamines by a number of well-known methods, and many are readily available from commercial sources.

As previously mentioned, in certain aspects of the subject matter, one or more components of the composition, such as the bodying component, can be a non-acrylic based bodying component. A wide variety of non-acrylic based components can be used. Non-limiting examples include polyolefins, polyvinylarenes, polyurethanes, polycarbonates, polyesters, polyethers, and combinations of these, possibly in combination with one or more other agents and/or components. A specific non-limiting example of polyvinyl aromatic is polystyrene.

additive

Various additives and initiators are useful in conjunction with the subject adhesives and compositions. Sometimes the term "curing agent" is used herein. The term refers to an agent(s) or stimulus that promotes or causes polymerization of the polymer(s) in the subject composition. Thus, the term fixative includes a single agent, a single stimulus, multiple agents, multiple stimuli, a combination of agents, a combination of stimuli, and a combination of one or more agents and one or more stimuli. In general, the curing agent(s) can be activated by at least one of radiation, heat, moisture, pressure, ultrasound, exposure to chemical agents, and combinations thereof. Generally, the term curing agent as used herein refers to a catalyst and/or a photoinitiator. However, it should be recognized that the term can include a wide variety of other agents (and stimuli).

hot catalyst. Catalysts herein may be external or internal. The catalyst can be used in an amount of 0-10 wt%, 0.1-10 wt%, 0-5 wt%, 0.1-5 wt%, 0-4 wt%, 0.1-4 wt%, 0-2 wt%, 0.1-2 wt%, or 0.01-2 wt% . Suitable catalysts include blocked strong acid catalysts based on acids consisting of, for example, trifluoromethanesulfonic acid (triflicacid), dinonylnaphthalenesulfonic acid (DSA), dinonylnaphthalene disulfonic acid (DDSA), Hexafluorophosphoric acid and antimony ammonium hexafluoride (Lewis acid), and are available from King Industries, e.g. CXC1615 (diethylamine salt of trifluoromethanesulfonic acid), 155 (blocked acid catalyst based on DNNDSA), CXC1612 (antimony ammonium hexafluoride), Super-A218 (zinc salt of trifluoromethanesulfonic acid), CXC1738 (ammonium hexafluorophosphate) and CXC1614 (ammonium triflate).

The base catalyst can be a primary, secondary or tertiary amine. A suitable primary diamine is diaminodiphenylsulfone. Other bases include imidazoles and ketimines. Suitable imidazoles include 2-methylimidazole, 2-ethyl 4-methylimidazole, 2-phenylimidazole. A list of imidazole curing agents can be found in paragraph US Patent Application Publication No. 2009/0194320. A possible alkaline curing agent is dicyandiamide [DICY].

Photoinitiator. Photoinitiators include free radical photoinitiators and UV free radical photoinitiators. Photoinitiators may be present in the subject compositions in an amount of 0-10 wt%, 0.01-10 wt%, 2-5 wt%, or 1-3 wt%.

Free radical photoinitiator. Thermal initiators include tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, benzoyl peroxide, tert-benzoyl peroxide Amyl esters, tert-butyl peroxyacetate, and azo compounds sold under the trade name Vazo such as, for example, Vazo52, Vazo67 and Vazo88.

UV free radical photoinitiator. Photoinitiators suitable for the present subject matter include both Type I and Type II photoinitiators.

Type I photoinitiators are defined as undergoing essentially unimolecular bond cleavage reactions upon irradiation, thereby gaining free radicals. Suitable type I photoinitiators are selected from the group consisting of benzoin ethers, benzil ketals, alpha-dialkoxy-acetophenones, alpha-hydroxyalkyl phenones and acyl-phosphine oxides. Suitable type I photoinitiators are commercially available, eg Esacure KIP100 from Lamberti Spa, Gallarate, Italy, or Irgacure 651 from Ciba-Geigy, Lautertal, Germany.

In general, suitable Type I photoinitiator compounds herein are selected from the group consisting of benzoin ethers, benzil ketals, alpha-dialkoxy-acetophenones, alpha-hydroxyalkyl phenones and acyl-phosphine oxides.

Type II photoinitiators are defined as essentially undergoing a bimolecular reaction in which the photoinitiator, in an excited state, interacts with a second compound acting as a co-initiator to generate free radicals. Suitable type II photoinitiators are selected from benzophenones, thioxanthones and titanocenes. Suitable co-initiators are preferably selected from amine functional monomers, oligomers or polymers, whereby amino functional monomers and oligomers are used in certain embodiments. Primary, secondary, and tertiary amines can be used, whereby tertiary amines are used in certain embodiments. Suitable Type II photoinitiators are commercially available, such as Esacure TZT from Lamberti Spa, Gallarate, Italy, or 2- or 3-methylbenzophenone from Aldrich Co., Milwaukee, Wisconsin, USA. Suitable amine co-initiators are commercially available, e.g. from Rahn AG, Zurich, Switzerland 5275.

Specific examples of Type II photoinitiator compounds include benzophenones and thioxanthones. In specific embodiments, co-initiator compounds such as amines may be present and may interact with the Type II photoinitiator compound.

crosslinking agent. Useful crosslinkers herein include radiation-activatable crosslinkers selected from the group consisting of aldehydes, ketones, quinones, thioxanthones, and s-triazines. Metal chelate crosslinker catalysts are also contemplated. Crosslinking agent can be 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% % is present in the subject compositions.

Photosensitizer. Each sensitizer tends to have its own characteristic response in the visible and ultraviolet spectra, such that they can be used in combination to amplify the light of response, and/or increase the speed of response to light exposure.

The photosensitizer can be, for example, 0-15wt%, 0.01-15wt%, 0-10wt%, 0.01-10wt%, 0-5wt%, 0.01-5wt%, 0-2wt%, 0.01-2wt%, 0-1wt%, and Amounts of 0.01-1% by weight are used in the subject compositions. A photosensitizer can be a sensitizing dye.

Exemplary sensitizing dyes are those of the following classes: diphenylmethane, xanthene, acridine, methine and polymethine, thiazole, thiazine, azine, aminoketone, porphyrin, chromatic aromatic poly Cyclic hydrocarbons, thioxanthones, p-substituted aminostyryls and aminotriarylmethanes.

Stabilizers and processing aids. Several classes of stabilizers and processing aids are contemplated, including oils/waxes, antioxidants, photosensitizers, rheology modifiers, fillers, free radical structural components, ring-opening structural components, epoxies, oxa Cyclobutane, anhydride, lactam, lactone, Azolines, isocyanates, bismaleimides and azodioxides. Stabilizers and processing aids are used in the subject composition in amounts such as 0-10 wt%, 0.1-10 wt%, 0-4 wt%, 0.1-4 wt%, 0-3 wt% and 0.1-3 wt%. In certain embodiments, it is useful to use azodioxide as a stabilizer. One such example is a stabilizer commercially available under the designation UVTS-52 from Hampford Research, Inc. of Stratford, CT. UVTS-52 is a thermally reversible azodioxide. UVTS-52 (CAS34122-40-2) is considered to be 1,4,4-trimethyl-2,3-diazabicyclo-[3.2.2]-non-2-ene-2,3-dioxide things.

Plasticizers - oils and waxes. Suitable plasticizers include plasticizing oils, such as mineral oil, but also olefin oligomers and low molecular weight polymers, or glycol esters of benzoates, and also vegetable and animal oils and derivatives of such oils. Petroleum derived oils that may be used are relatively high boiling temperature materials containing only a small proportion of aromatic hydrocarbons. In this regard, aromatics should in certain embodiments be less than 30%, and more specifically less than 15%, by weight of the oil. Alternatively, the oil can be completely non-aromatic. Suitable oligomers included as plasticizers may be polypropylene, polybutene, hydrogenated polyisoprene, hydrogenated butadiene or the like having an average molecular weight between about 100 and about 10,000 g/mol . Suitable vegetable and animal oils include glycerol esters of common fatty acids (eg, stearic acid, oleic acid, linoleic acid, linolenic acid) and polymerization products thereof. Other plasticizers may be used provided they have suitable compatibility. Naphthenic mineral oils manufactured by Nynas Corporation have also been found 222B is a suitable plasticizer. As will be appreciated, plasticizers are generally used to reduce the viscosity of the overall adhesive composition without substantially reducing the adhesive strength and/or the use temperature of the adhesive. The choice of plasticizer is useful in formulation for a specific end use, such as a wet strength core application. Because of economics related to production and material costs, the amount of plasticizer in the adhesive should be maximized for cost considerations, since the cost of plasticizers is usually lower than other materials in the formulation such as polymers and adhesive resins.

Waxes can also be used in the adhesive composition in an amount of 0% to 20% by weight, or 0.1-20 wt%, or 0.1-15 wt%, and are used to reduce the melt viscosity of the adhesive without significantly reducing its tackiness. Adhesive bonding characteristics. These waxes also serve to reduce the open time of the composition without affecting temperature performance.

Examples of useful wax materials include the following.

It is possible to use low molecular weight (100-6000 g/mol) polyethylenes having hardness values from about 0.1 to 120 and ASTM softening points from about 66°C to 120°C as determined by ASTM method D-1321.

Petroleum waxes such as paraffin waxes having a melting point of from about 130°F to 170°F and microcrystalline waxes having a melting point of from about 135°F to 200°F as determined by ASTM method D127-60 may be used.

It is possible to use atactic polypropylene with a ring and ball softening point from about 120° to 160°C.

It is possible to use a metallocene-catalyzed propylene-type wax commercialized under the name "Licocene" by Clariant International, Ltd., Muttenz, Switzerland.

It is possible to use metallocene-catalyzed waxes or single-site-catalyzed waxes, such as those described, for example, in US Patents 4,914,253 and 6,319,979, and WO97/33921 and WO98/03603.

Possibility to use paraffin waxes, microcrystalline waxes, polyethylene waxes, polypropylene waxes, by-product polyethylene waxes, synthetic waxes produced by polymerizing carbon monoxide and hydrogen such as Fischer-Tropsch waxes, oxidized Fischer-Tropsch waxes, functionalized Waxes and mixtures thereof.

Polyolefin wax. As used herein, the term "polyolefin wax" refers to those polymers or long-chain entities composed of olefin monomer units. These materials are commercially available from Westlake Chemical Co. under the trade name "Epolene".

Materials used in certain embodiments of the present subject matter have a ring and ball softening point of 200°F to 350°F. As should be understood, each of these waxes is solid at room temperature. Other useful substances include hydrogenated animal, fish and vegetable fats and oils, such as hydrogenated tallow, lard, soybean oil, cottonseed oil, castor oil, herring oil, cod liver oil, etc., and because they are hydrogenated they are solid at ambient temperature , which was found to be useful for use as a wax material equivalent. These hydrogenated materials are often referred to in the adhesive industry as "animal or vegetable waxes".

Antioxidants. The adhesive also typically includes from about 0.1% to about 5% of a stabilizer or antioxidant. Stabilizers useful in the subject adhesive compositions are incorporated to help protect the above-mentioned polymers, and thereby protect the overall adhesive system, from thermal and oxidative degradation that typically occur in adhesives. Occurs during the manufacture and application of the adhesive and during normal exposure of the final product to the atmosphere. This degradation is usually evidenced by deterioration in the adhesive's appearance, physical properties, and performance characteristics. In certain embodiments, a particularly useful antioxidant is Irganox 1010, tetrakis(methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate))methane manufactured by Ciba-Geigya. Among the applicable stabilizers are high molecular weight hindered phenols and polyfunctional phenols, such as sulfur and phosphorus containing phenols. Hindered phenols are well known to those skilled in the art and can be characterized as phenolic compounds that also contain sterically bulky radicals in close proximity to their phenolic hydroxyl groups. In particular, a tert-butyl group is generally substituted in at least one ortho position on the benzene ring relative to the phenolic hydroxyl group. The presence of these sterically bulky substituent groups in the vicinity of the hydroxyl group serves to prevent its stretching frequency, and correspondingly its reactivity. This steric hindrance thus provides phenolic compounds with their stabilizing properties. Representative hindered phenols include:

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

Pentaerythritol tetrakis-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate;

n-octadecyl-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate;

4,4'-methylenebis(4-methyl-6-tert-butylphenol);

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

2,6-di-tert-butylphenol;

6-(4-hydroxyphenoxy)-2,4-bis(n-octylthio)-l,3,5-triazine;

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

Di-n-octadecyl-3,5-di-tert-butyl-4-hydroxyphenyl phosphate;

2-(n-octylthio)ethyl-3,5-di-tert-butyl-4-hydroxybenzoate; and

Sorbitan hexa-(3,3,5-di-tert-butyl-4-hydroxy-phenyl)propionate.

The performance of these stabilizers can be further enhanced by using in combination with: (1) synergists such as, for example, dilauryl thiodipropionate and phosphites; and (2) chelating agents and metal deactivators , such as, for example, ethylenediaminetetraacetic acid, its salts, and disalicylalpropylenediimine.

UV inhibitors. Antioxidants can be used to prevent oxidative attack on the adhesive composition, which can lead to loss of adhesive strength and internal bond strength of the adhesive composition. Useful antioxidants include, but are not limited to, amines such as N-N'-di-β-naphthyl-1,4-phenylenediamine available as AGERITED, phenolic compounds such as SANTOVARA from Monsanto Chemical Co. 2,5-Di-(t-amyl)hydroquinone, tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl available as IRGANOX 1010 from Ciba-Geigy Corp. ) ethylene propionate] methane, and 2-2'-methylenebis(4-methyl-6-tert-butylphenol), available as ANTIOXIDANT 2246, and dithiocarbamate, such as dithiocarbamate Zinc butyl carbamate.

Rheology modifier. Rheology modifiers can be added to alter the thixotropic properties of the composition. Suitable rheology modifiers include polyamide waxes, fumed silica, flow control additives, reactive diluents, anti-settling agents, alpha-olefins, hydroxyl-terminated siloxane-organic copolymers, including but not limited to Hydroxyl-terminated polyoxypropylene-dimethylsiloxane copolymers and combinations thereof.

filler. Fillers can be used to impart strength or reduce overall cost. Useful fillers herein include aluminum trihydroxide, calcium hydroxide, the trade name Expandable microspheres, carbon black, titanium dioxide, or nickel-coated glass spheres are sold.

In some forms of the subject matter, fillers, rheology modifiers and/or pigments are present in the adhesive. These can perform several functions, such as altering the rheology of the adhesive in a desired manner, absorbing moisture or oil from the adhesive or the substrate to which it is applied, and/or promoting cohesive rather than cohesive failure. Other examples of such materials include calcium carbonate, calcium oxide, talc, coal tar, textile fibers, glass particles or fibers, aramid pulp, boron fibers, carbon fibers, silicate minerals, mica, powdered quartz, bentonite, silica fume stone, kaolin, fumed silica, silica aerogel, or metal powders such as aluminum powder or iron powder. Of these, calcium carbonate, talc, calcium oxide, fumed silica, and wollastonite are especially useful, alone or in some combination, as these generally promote the desired cohesive failure mode.

In addition to the various specific compositions described herein, the subject matter also provides several additional specific compositions as explained below. It should be recognized that these are representative, non-limiting examples of other specific compositions of the subject matter.

Additional embodiments of the present subject matter include suitably cured pressure sensitive adhesives comprising: (a) 50-80 wt% of an acrylic base polymer having a Mw of 250,000-750,000, (b) 20-40 wt% of a or multiple structural diluents, (c) 0-30wt% optional acrylic-epoxy functional component, (d) 0-0.5wt% metal chelate crosslinker, and (e) 0-2wt% % of one or more external catalysts.

Another embodiment of the present subject matter is a curable pressure sensitive adhesive formed from a blend, wherein the blend includes (a) a random copolymer of high molecular weight (e.g., 400-600 kg/mol), It includes (i) alkyl acrylate base monomers; (ii) vinyl acetate; (iii) methyl acrylate; (iv) acrylic acid; and (v) silane crosslinking monomers; - 50 kg/mol) of random copolymers comprising (i) linear alkyl acrylate base monomers, (ii) branched chain alkyl acrylate base monomers and (iii) epoxy-functional methacrylate monomers (c) oligomers such as STPE-30 from Wacker; (d) acrylate-glycidyl esters of 10-carbon carboxylic acids; (e) cationic reactive diluents such as trimethylolpropaneoxa Cyclobutane (TMPO); (f) high molecular weight acid functional acrylic diluent monomer, (an example of which is 2-acryloyloxypropyl phthalate); (g) bisphenol-A type epoxy resin , which is semisolid at room temperature; and (h) a crosslinker and a silane catalyst such as aluminum acetylacetonate.

The subject matter also provides methods and techniques for conjugation using the liquids and compositions described herein. Figure 2 schematically depicts a bonding method 300 according to the present subject matter. In method 300 , a layer or coating 310 of a composition as described herein is applied to a substrate or film of interest 320 . The composition may be applied using various techniques such as spraying or coating as generally described at operation 330 . The coated or otherwise applied composition is then rendered tacky by exposure to, for example, UV radiation, as shown at 340 in FIG. 2 . In this state, the composition is often referred to as "A-staged" and, in certain embodiments, can exhibit a T-peel value of 0.17 lbs and a 180° peel of 0.64 lbs. Another layer of material such as a laminate of copper and aluminum foil as shown at 350 is then contacted with the adhesive A-stage composition 310 . The resulting layered assembly involves one or more processing stations such as laser patterning station 360 that form a patterned laminate as depicted at 370 in FIG. 2 . Depending on end use requirements, additional processing such as foil matrix removal, such as collection of waste matrix 380 at operation 375, may be performed. The resulting processed laminate is shown at 385. The processed laminate 385 may then undergo one or more additional processing operations, such as thermal curing shown at 390 . After heat curing, the composition 310 is referred to as "B-staged," which generally exhibits significantly greater T-peel and 180° peel values than those of its A-stage. For example, the T-peel value for the B-stage can be about 0.37 lbs and the 180° peel value can be about 3.6 lbs. The cured product can be collected in roll form or sheet form 395 .

In general, in various embodiments of the present subject matter, a liquid or composition described herein may exhibit viscosity or exhibit a viscosity commonly associated with pressure sensitivity when the composition is at least partially cured by any of the agents or stimuli as described herein. Adhesive related properties. In some forms, the first or partial cure is achieved by exposing the composition to UV radiation, electron beam, heat, or a combination of these. Additionally, the partially cured composition can then be further cured by exposure to heat, chemical agents including water or moisture, pressure, or a combination thereof.

The subject compositions can be used in a wide variety of applications. For example, a specific use application may involve foam articles made from the compositions described herein. One or more conventional foaming agents can be incorporated into the subject compositions to foam or expand to produce a foam layer or article. The composition can also be used to adhesively bond the foam article to other surfaces, substrates or objects.

More specifically, the subject matter can be used to bond or otherwise attach film to film, film to foil, apron to foil, apron to film, fabric to fabric, fabric to virtually any other material or substrate such as film, paper, and metal, paper and metal, metal and metal, film and other plastic, plastic and plastic, and combinations of these and other surfaces, materials and/or substrates. The subject matter can also be used to provide chemical resistance, such as corrosion resistance, to various surfaces and substrates. For example, the subject matter can be used to provide chemically resistant labels, and solvent resistant laminates such as solvent resistant glass and foil assemblies. The subject matter can also be used to form film laminates, such as film-to-film laminates. Another contemplated application of the subject matter is the field of shrink sleeves and shrink sleeve labels. Furthermore, this topic can be broadly applied to the solvent welding of two-layer films. Yet another field of application relates to the corrosion protection of components, and especially metal pipes such as oil and gas pipes. The subject compositions and methods can be used to provide or increase resistance to impact forces, structural integrity, and protection against corrosion or exposure to environmental elements. A specific and non-limiting example of such corrosion protection is to provide an outer layer, an inner layer, or along both the outer and/or inner circumferential surface of the pipe. Another significant benefit of certain compositions according to the present subject matter is that the compositions can be subjected to bending, flexing, or other stress without cracking. This is desirable if, for example, the composition(s) are applied to the conduit. Still another contemplated application of certain compositions of the subject matter is the formation of fiberglass structures such as marine vessel hulls, certain sporting goods, and structural components. Still another application of the subject matter is a "roll-on, take-off" (ROSO) application.

Example

Example 1-4

Properly cured adhesives of certain embodiments of the subject matter can be described as acrylic polymers mixed with reactive diluents, oligomers, and structural components. Additional details of the subject matter are provided in the Examples below.

Example 1: High Performance PSA with Moisture Curable Oligomer (Properly Cured Adhesive)

Example 1 is an acrylic polymer with a potentially reactive oligomer (STPE-30). STPE-30 oligomers cure by silane-silane condensation reactions. Optionally, the base polymer may also have silane functionality and be co-reacted with reactive oligomers.

Example 2: High Performance PSA with UV Curable Oligomers (Properly Cured Adhesives)

Example 2 is an acrylic polymer mixed with a reactive diluent and structural components that is triggered by UV exposure to convert the adhesive from a liquid to a solid PSA and cured to full strength by heat during film to film lamination .

To incorporate in-situ moisture curing into high-performance pressure-sensitive adhesive systems, acrylic polymers, tackifiers, and reactive oligomers are mixed in a solvent. After application as described herein and exposure to humidity, the system is coated in tape form under conditions that cause a portion of the oligomers to potentially react.

Example 3: High Performance PSA with Moisture Curable Oligomers (Properly Cured Adhesive, Solid Component)

The composition of Example 3 is a high performance PSA with a moisture curable oligomer (properly cured adhesive). To incorporate in-situ moisture curing into high-performance pressure-sensitive adhesive systems, acrylic polymers, tackifiers, and reactive oligomers are mixed or otherwise combined in a solvent. After application and exposure to humidity, the system is coated in tape form under conditions that lead to a potential reaction of a portion of the oligomers.

Table 3: Composition of Example 3PSA

weight percent components 54.45% DEV-8631 U (acrylic base polymer) 25% Terpene phenolic tackifier (softening point 110-120°C) 20% Terpene phenolic tackifier (softening point 110-120°C) 0.55% Metal Chelate Aluminum Acetylacetonate (Crosslinker & Catalyst)

Acrylic base polymers are high molecular weight (400-600 kg/mol) random copolymers comprising (a) alkyl acrylate base monomers; (b) vinyl acetate; (c) methyl acrylate; (d) acrylic acid and (e) a silane crosslinking monomer.

An example of an acrylic base polymer is DEV8631U, which is a random copolymer having a molecular weight (Mw) of about 518,000 g/mol, comprising the following ingredients.

Table 4: Acrylic base polymer (ie DEV8631U) in the Example 3 PSA

components weight percent 2-Ethylhexyl Acrylate (Basic Monomer) 57.95 Vinyl acetate (modified monomer) 25 Methyl acrylate 15 Acrylic acid (high Tg monomer, crosslinking sites) 3 Methacryloxypropyltrimethoxysilane (crosslinking monomer) 0.05

Reactive oligomers are silane terminated polyethers (oligomers) such as STPE-30 from Wacker shown below as formula (22). STPE-30 is a silane terminated polyether. The two silane-terminated polypropylene glycols shown are based on the same polyether. The difference lies in the end groups.

The crosslinker and catalyst is aluminum acetylacetonate and is shown as formula (23) below:

The bonding method is depicted in FIG. 6 . Referring to FIG. 6 , in general, a bonding method 200 according to the present subject matter is as follows. In operation 210, a composition as described herein is coated or otherwise applied to a film or substrate. An example of such a film is a release film. After suitable application, the composition is dried, which typically also includes removal of at least a portion of any solvent in the composition, as depicted by operation 220 . Representative conditions for drying include exposure to 80°C for about 5 minutes. In operation 230 , the composition is then suitably cured by exposure to heat and/or humidity to form high strength adhesive 240 . The condensation reaction that occurs is shown below:

～Si-OCH ₃ +H ₂ O→～Si-O-Si～+CH ₃ OH

Figure 1 depicts the dynamic mechanical analysis of the properly cured pressure sensitive adhesive of Example 3.

Example 4: Liquid composition curable to PSA (UV) and B-staged during film-to-film lamination (properly cured adhesive)

In Example 4, an acrylic polymer was mixed with a reactive addition diluent and a structural diluent.

Table 5: Composition of the Liquid Composition of Example 4

weight percent components 15% ACE Monomer Phase Component (Reactive Diluent) 10% V2100 (reactive thinner) 10% Epon 834 (structural component) 9% TMPO oxetane (structural component) 56% EB14-04 (acrylic polymer)

An example of a reactive diluent is the ACE monomer ACE ^™ hydroxyacrylate monomer supplied by Momentive Performance Materials, Leverkusen Germany, which is the reaction product of acrylic acid and Cardura ^™ . Cardura is the glycidyl ester of Versatic ^™ Acid 10, a highly branched saturated carboxylic acid containing 10 carbon atoms. ACE has a unique structure combining a bulky hydrophobic tail, pendant hydroxyl groups, and acrylate functional groups, with a molecular weight of approximately 300. ACE has the structure shown below as formula (24):

Another reactant diluent, a high molecular weight acid functional acrylic diluent monomer V-2100, which is 2-acryloyloxypropyl phthalate available from SanEsters Corporation, New York, is shown below as formula (25 ):

The structural component is EPON ^™ Resin 834, a BPA-based epoxy resin available from Momentive Performance Materials that is semi-solid at room temperature. Systems using EPON Resin 834 can be formulated for use in a variety of high solids and tar modified coatings, high tenacity adhesives, laminates and prepregs. Because of its higher molecular weight, EPON Resin 834 offers increased system reactivity, surface adhesion, and cured resin toughness compared to liquid grade BPA epoxy resins, but reduced elevated temperature performance. EPON Resin 834 is especially useful in applications requiring additional surface adhesion, cure speed or toughness.

Another structural component is a cationic reactive diluent, such as trimethylolpropane oxetane (TMPO). UV/EB cationic formulations can be formed and mainly include resins, diluents and photoinitiators, such as 3,4 epoxycyclohexylmethyl-3,4 epoxycyclohexane carboxylic acid (shown below as Formula (26)) and TMPO as reactive diluent:

The acrylic component is a low molecular weight (20-50 kg/mol) random copolymer comprising (a) a linear alkyl acrylate base monomer, (b) a branched alkyl acrylate base monomer and (c) a ring Oxygen functional methacrylate monomer.

An example of an acrylic component is the following low molecular weight polymer EB14-04, which is a random copolymer with a Mw of about 40,000 g/mol:

Table 6: Example of acrylic component, EB14-04 in the liquid composition of Example 4

components weight percent Butyl Acrylate (Basic Monomer) 40 tert-butyl acrylate 40 S-100 (Cycloaliphatic Epoxy Functional Methacrylate Monomer) 30

The bonding method is depicted in FIG. 6 .

Example 5-7

Examples 5-7 illustrate polymerization methods that can be used to form the subject components and compositions.

Example 5: Polymerization of Components with Pseudo-Telechelics Using SFRP Reagents with Epoxy Functionality

Acrylic copolymers having reactive functionality located in segments adjacent to the ends of the polymer chains, shown below as formula (27), are prepared as follows:

A 1500 ml reactor equipped with heating mantle, stirrer, reflux condenser, feed tank and nitrogen inlet was fed with 8.30 g of Blocbuilder from Arkema Inc. Monomer and solvent were added to the feed vessel in the following amounts:

22.30 g of 2-ethylhexyl acrylate;

64.30 g of ethoxyethoxyethyl acrylate; and

85.30 g of propyl acetate

The Blocbuilder in the reactor and the monomer and solvent in the feed vessel were purged with a constant nitrogen bubble for 30 minutes at room temperature. After this hold, the monomer and solvent mixture was fed to the reactor to create a small portion of non-reactive segment adjacent to the active polymer pattern in order to add acrylate groups to the Blocbuilder. The reactor feed mixture was then heated to greater than 70°C (reactor jacket 75°C) and held for 30 min. After the second hold, the reactor feed mixture was cooled to room temperature (about 25°C). Once the reactor feed reached room temperature, 13.40 g of Synasia Epoxy S-100 was fed to the reactor. After the addition of the epoxy resin, the reactor was sealed and purged with a constant nitrogen bubble for an additional 30 minutes at room temperature. After 30 minutes of bubbling, the reactor mixture was heated to 100°C. When the reactor mixture was heated to 100°C, 579.10 g of ethoxyethoxyethyl acrylate and 201.10 g of 2-ethylhexyl acrylate were fed to the feed vessel and purged with a constant nitrogen bubble . When the reactor mixture reached 100°C, the time was set to zero (T=0). At T = 15 minutes, a sample was taken for gas chromatographic analysis to check monomer conversion. When monomer conversion is confirmed (approximately 30 minutes, T=45), the reactor mixture is maintained at a temperature between 110°C and 117°C under reflux until >90% of the converted epoxy resin (approximately 70% of 2-EHA and EOEOEA conversion). At this transition, the reagent feed mixture with an active nitrogen purge was added to the reactor during 180 minutes. During the reagent feed, the temperature of the reaction was maintained at 110-118°C under reflux. After the reagent feed was complete, the reaction conditions were maintained until 80% conversion of 2-EHA and EOEOEA was achieved. This is to generate the remainder of the non-reactive segment adjacent to the functional end segment. At this transition, 13.40 g of Synasia Epoxy S-100 and 13.40 g of propyl acetate were rapidly fed into the reactor (about 2 min.) to produce the final functional end-block. Reaction conditions were maintained until greater than 98% conversion of 2-EHA and EOEOEA was achieved. The resulting solution polymer was then cooled to ambient temperature and discharged from the reactor. The overall theoretical Mn of the polymer is 41,000 g/mol. Each non-reactive middle segment is 32,000 g/mol and the functional end segment is 4,500 g/mol.

The measured molecular weight (Mn) of the total acrylic polymer was 20,043 g/mol (determined by gel permeation chromatography relative to polystyrene standards) and the polydispersity was 3.02. So the calculated Mw is 60,530 g/mole.

Example 6: Polymerization with a single functional end block (tadpole) Example with alcohol functionality using SFRP reagents

Acrylic copolymers with reactive functionality located in segments adjacent to the ends of the polymer chains, shown as (28), are prepared as follows:

A 1500ml reactor equipped with heating mantle, stirrer, reflux condenser, feed tank and nitrogen inlet was fed with 11.41g of Blocbuilder. Monomer and solvent were added to the feed vessel in the following amounts:

105.93 g of n-butyl acrylate;

26.48 g of tert-butyl acrylate; and

17.26 g of 4-hydroxypropyl acrylate

The Blocbuilder in the reactor and the monomer and solvent in the feed vessel were purged with a constant nitrogen bubble for 30 minutes at room temperature. After this hold, the monomer and solvent mixture was fed to the reactor to create a small reactive segment adjacent to the active polymer pattern in order to add acrylate groups to the Blocbuilder. The reactor feed mixture was then heated to greater than 70°C (reactor jacket 75°C) and held for 30 min. After the second hold, the reactor mixture was heated to 100°C. While the reactor mixture was heated to 100°C, 1071.14 g of butyl acrylate and 267.78 g of t-butyl acrylate were fed to the feed vessel and purged with a constant nitrogen sparge. When the reactor mixture reached 100°C, the timer was set to zero (T=0) and held between 100 and 105°C. At T = 15 minutes, a sample was taken for gas chromatographic analysis to check monomer conversion. When monomer conversion was confirmed (approximately 30 minutes, T=45), the reactor mixture was maintained at temperatures between 100°C and 105°C until >80% butyl acrylate was converted. At this transition, the reagent feed mixture with an active nitrogen purge was added to the reactor over a period of 180 minutes. During the reagent feed, the temperature of the reaction was maintained between 100-105°C. After completion of the reagent feed, the reaction conditions were maintained until greater than 98% conversion of butyl acrylate was achieved. The resulting polymer was then cooled to ambient temperature and discharged from the reactor. The overall theoretical Mn of the polymer is 50,000 g/mol. Each non-reactive segment is 45,000 g/mol and the functional end segment is 5,000 g/mol.

The measured molecular weight (Mn) of the total acrylic polymer was 53,591 g/mol (determined by gel permeation chromatography relative to polystyrene standards) and the polydispersity was 1.51. So the calculated Mw is 80,922.

Example 7: Example of Random Functional Distribution with Alcohol Functionality

Acrylic copolymers with reactive functionality randomly located throughout the polymer chain, generally shown as (29), are prepared as follows:

A 1500 ml reactor equipped with heating mantle, stirrer, reflux condenser, feed tank and nitrogen inlet was fed with 139.37 g of toluene. Monomers were added to the feed vessel in the following amounts:

83.16 g of 2-ethylhexyl acrylate;

239.51 g of ethoxyethoxyethyl acrylate; and

9.98g of 4-hydroxypropyl acrylate

Solvent and initiator were added to the second feed vessel in the following amounts:

3.33 g of lauryl peroxide; and

30.00g of toluene

The toluene in the reactor, the initiator mixture in the feed vessel, and the monomers were purged with a constant nitrogen bubble for 30 minutes at room temperature. After this hold, the toluene in the reactor was heated to 105°C with a small amount of reflux leaving the condenser. At this point, the monomer and initiator mixture was fed to the reactor over 90 minutes. During the reagent and initiator feeds, the reactor mixture was maintained at a temperature between 105°C and 116°C under reflux. After the reagent and initiator feeds were complete, the reaction conditions were maintained for 60 minutes. During the 60 minute hold, a cook-off catalyst charge was prepared in the feed vessel. The deflagration catalyst charge consisted of 24.28 g of toluene and 0.37 g of pivalate peroxypivalate. The deflagration catalyst was bubbled for 15 minutes under a constant nitrogen purge. After the 60 minute hold, the deflagration catalyst was fed to the reactor within 30 minutes. Once the deflagration catalyst charge was consumed, the reaction was maintained at >110°C for 60 minutes. The resulting solution polymer was then cooled to ambient temperature and discharged from the reactor.

The measured molecular weight (Mn) of the total acrylic polymer was 13,301 g/mol (determined by gel permeation chromatography relative to polystyrene standards) and the polydispersity was 2.76. So the calculated Mw is 36,711.

Example 8-39

Examples 8-33 are based on an acrylic polymer mixed with a reactive diluent and a structural component, which is triggered by UV exposure to convert the adhesive from a liquid to a solid PSA, and cured to full strength (structure) by heating.

Examples 8-33 are illustrated in Table 7.

Table 7: Examples 8-33 of Adhesive Compositions

In Table 7, IR means impact resistance, measured according to ASTM-G14-04 (2010). Rolling ball tack was determined according to ASTM-D3121-06.

Examples 34-36 illustrate lap shear and rolling ball tack measurements of additional adhesive compositions of the subject matter.

Example 34 is an acrylic polymer mixed with structural components and dried with mild heat to a PSA and then fully cured by higher heat triggers to create a structural bond between the two substrates.

Example 35 is an acrylic polymer blended with both a reactive oligomer and a structural component, and dried with mild heat to a PSA, and then a full cure is triggered by higher heat to create a structural bond between the two substrates .

Example 36 is an acrylic polymer mixed with a reactive diluent and a structural component that is triggered by low heat exposure to convert the adhesive from a liquid to a PSA and cured to full strength (structural) by higher heat.

Example 34: AS-2549 acrylic PSA was crosslinked with AAA and mixed with Synasia S-21 epoxy resin and dried gently at 90°C for 10 min to cast a solvent free PSA film. Initiators used for thermal curing of epoxy resins are mostly inactive at temperatures less than 95°C. After drying the film to produce the PSA tape, the tape can be applied to a given substrate desired to be bonded. Once the tape is applied, additional heat is applied to initiate conversion of the adhesive to sufficient strength. Structural bonds were formed at 140°C for 15 minutes. A depiction of the lap shear test of Example 34 is shown in FIG. 3 . The procedure is as follows:

The lap shear data (Al and Al) for Example 34 are presented in Table 8.

Table 8: Lap Shear Data

Lap shear was determined as follows. ASTM D-1002 Standard Test Method for Apparent Shear Strength (Metal to Metal) of Adhesively Bonded Metal Specimens by Single Lap Joint Connections Under Tensile Load (Ref.). Adhesive thickness is 0.0024 inches +/- 0.0006 inches. The load is 1 inch/minute. Measure peak load.

Example 35: AS-2549 acrylic PSA was crosslinked with AAA and mixed with Synasia S-21 epoxy resin and KH4-67 and dried gently at 90°C for 10 min to cast a solvent free PSA film. Initiators for thermal curing of epoxy resins are mostly inactive at temperatures less than 95°C. After drying the film to produce the PSA tape, the tape can be applied to the desired substrates to be bonded. Once the tape is applied, additional heat is applied to initiate the conversion of the adhesive to full strength. Structural bonds were formed at 140°C for 15 minutes. Figure 4 depicts the procedure for the lap shear test in Example 35.

The lap shear data (Al and Al) for Example 35 are presented in Table 9.

Table 9: Lap Shear Data

Example 36: KH4-105 acrylic oligomer mixed with EPON 828 epoxy resin, TMPO and Siloquest A-187. It was cured gently at 110°C for 7 min to cast the PSA film. Initiators for thermal curing of epoxy resins are very slow at temperatures less than 110°C. After drying the film to produce the PSA tape, the tape can be applied to the desired substrates to be bonded. Once the tape is applied, additional heat is applied to initiate conversion of the adhesive to sufficient strength. Structural bonds were formed at 140°C for 15 minutes.

The lap shear data (Al and Al) for Example 36 are presented in Table 10.

Table 10: Rolling Ball Tack Data for Example 36

Example 37: A liquid according to the present subject matter is applied to a substrate and then suitably cured by exposure to actinic radiation. The diagram is depicted in FIG. 5 . In particular, Figure 5 schematically depicts the application of a liquid or other composition to a film, label and/or container, and exposure to actinic radiation to properly cure the liquid or composition. A source of film or label 10 having a liquid or composition 20 coated area, face or surface as described herein is provided. In certain embodiments, one or more areas 25 or strips 30 of tacky adhesive may be provided to aid in initially securing the film or label to the container of interest 40 . Before, during and/or after suitable application of the film or label to the container, actinic radiation 50 is directed to the coating, thereby adhering and/or curing the coating and producing the marked container 45 . This is generally indicated as operation A in FIG. 5 . After the initial application of the film or label, heat removal and/or application can be performed. Additional manipulations may be performed before, during and/or after the manipulation(s) A. FIG. 5 also schematically illustrates a continuous process 100 in which a plurality of containers 140 receive film or labels, which are exposed to actinic radiation within a closure 150 to produce a plurality of marked containers 145 .

Table 11 below includes exemplary formulations representing embodiments of the subject matter. The formulation includes a thickening component, a free radical addition diluent, a structural diluent and a photoinitiator and additives (i.e. 1010).

Table 11: Exemplary embodiments of adhesive compositions

Table 12 below shows selected performance data for some of the formulations in Table 11.

Table 12: Performance data for selected formulations in Table 11

Example 38: Two additional adhesive compositions according to the present subject matter are illustrated in Tables 13 and 14 below.

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

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

Example 39: Several additional compositions according to the present subject matter are illustrated in Tables 15 and 16 below. A particular application for these compositions is "roll-on-off-off" (ROSO) marking or related techniques.

Table 15: Roll tightening, tightening composition

Table 16: Roll tightening, tightening composition

Many other benefits will no doubt become apparent from future applications and developments of this technology.

All patents, published applications and articles mentioned herein are hereby incorporated by reference in their entirety.

The subject matter includes combinations of components and aspects of the various compositions described herein. Thus, for example, the subject matter includes one or more components and/or features of one embodiment in combination with one or more other components and/or features of other embodiment(s).

As described herein above, the present subject matter addresses many of the issues associated with previous policies, systems and/or devices. It should be appreciated, however, that those skilled in the art may make various changes in the details, materials, and arrangements of components that have been described and illustrated herein to explain the nature of the subject matter without departing from the principle and scope of the claimed subject matter, such as as expressed in the appended 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.