BR112020012160B1 - COMPOSITION COMPRISING A PRECURSOR AND A REACTING AGENT AND METHOD FOR FORMING A COMPOSITION - Google Patents

Abstract

The modification of functional groups along a polymer chain to make the groups activatable after exposure to actinic radiation is described. The polymers are typically architecture-controlled polymers. Adhesives containing the modified architectural polymers and related methods of use are also described.

Description

CROSS-REFERENCE TO RELATED ORDERS

[0001] The present application claims the benefit of U.S. Provisional Patent Application No. 62/607,437 filed on December 19, 2017, which is incorporated herein by reference in its entirety.

FIELD

[0002] The present invention relates to methods of modifying functional groups incorporated along a polymer backbone and/or pendant groups into UV-activatable groups. In many embodiments, the modification is performed using architectural polymers having functional groups at particular locations or regions along the backbone of the polymer. The present invention also relates to compositions, adhesives and pre-adhesive compositions containing the modified polymers, articles using the adhesives and systems for processing the adhesives.

BACKGROUND

[0003] Adhesives that are cured by exposure to UV radiation are known in the art. The use of controlled architecture polymers in adhesive formulations is also known and has been described by the Applicant. It is further known in the art that functional groups throughout many conventional polymers can be modified to be UV-activatable.

[0004] However, there is a need to form adhesive compositions using controlled architecture polymers that upon activation, such as exposure to UV radiation, exhibit particular properties and/or characteristics.

SUMMARY

[0005] Difficulties and drawbacks associated with prior approaches are addressed in the present invention in the following manner.

[0006] In one aspect, the present invention provides a composition comprising, consisting essentially of, or consisting of a precursor and a reacting agent. The precursor comprising at least one acrylic block copolymer, the at least one acrylic block copolymer comprising (i) a first molecular weight and position controlled reactive segment comprising at least one monomer having a functional group selected from the group consisting of into a self-reactive functional group, a reactive functional group, a non-reactive functional group and combinations thereof, and (ii) a second molecular weight and position controlled segment that includes at least one monomer with a functional group selected from the group consisting of a reactive functional group, a non-reactive functional group and combinations thereof. The reactive functionalities in the first reactive segment and the second segment can be the same or different from each other. The non-reactive functionalities in the first reactive segment and the second segment can be the same or different from each other. At least one of the functional groups of the at least one acrylic block copolymer may undergo a postpolymerization functionalization reaction with the reaction agent to make the at least one acrylic block copolymer crosslinkable upon exposure to actinic radiation. The at least one acrylic block copolymer is not crosslinkable after exposure to actinic radiation prior to the postpolymerization functionalization reaction. Notably, (i) the at least one acrylic block copolymer does not contain ethyl unsaturation along the polymer backbone and/or pendant groups, (ii) the reacting agent comprises at least one of a double bond and a functional group, being the functional group capable of reacting with at least one of the functional groups of the at least one acrylic block copolymer, (iii) the post-polymerization functionalization reaction is an acrylation reaction, and (iv) the post-polymerization functionalization reaction produces an ethyl unsaturated bond in the at least one acrylic block copolymer, the ethyl unsaturated bond being a double bond. The precursor forms a pre-adhesive composition after the post-polymerization functionalization reaction of the at least one acrylic block copolymer, and said pre-adhesive is at least partially cross-linkable upon exposure to actinic radiation to form an adhesive. The adhesive formed may be pressure sensitive adhesive. Actinic radiation is at least one of UV radiation and electron beam radiation.

[0007] In some embodiments, the first reactive segment comprises at least one monomer having a non-reactive functional group and at least one polymerizable comonomer having a cross-linkable functionality, the cross-linkable functionality comprising a self-reactive functional group and a reactive functional group while the second segment comprises at least one monomer having a reactive functional group and at least one monomer having a non-reactive functional group. In other embodiments, the first reactive segment comprises at least one monomer having a non-reactive functional group and at least one polymerizable comonomer having a cross-linkable functionality, the cross-linkable functionality comprising only a self-reactive functional group while the second segment comprises at least one monomer having only one non-reactive functional group. In still other embodiments, the first reactive segment comprises at least one monomer having a non-reactive functional group and at least one polymerizable comonomer having a crosslinkable functionality, the crosslinkable functionality comprising only one reactive functional group while the second segment comprises at least one monomer having only one non-reactive functional group.

[0008] Importantly, in all the embodiments described above of the invention, (i) the functional group of the at least one acrylic block copolymer undergoing the post-polymerization reaction may be the same or different from the functional group of the reaction agent, (ii ) at least one monomer with a non-reactive functional group within the first reactive segment and the second segment may be the same or different from each other, (iii) at least one monomer with a reactive functional group within the first reactive segment and the second segment may be the same or different from each other, (iv) the first reactive segment(s) include about 40% to about 99%, or about 45% to about 99%, or about 50% to about 99%, or about 55% to about 99%, or about 60% to about 99%, or about 65% to about 99%, or about 70% to about 99%, or about 75% to about 99%, or about 80% to about 99%, or about 85% to about 99%, or about 90% to about 99%, or about 95% to about 99% by weight of one or more non-reactive monomers, (v) the first reactive segment comprises about 40% to about 99%, or about 45% to about 99%, or about from 50% to about 99%, or about 55% to about 99%, or about 60% to about 99%, or about 65% to about 99%, or about 70% to about 99% 99%, or about 75% to about 99%, or about 80% to about 99%, or about 85% to about 99%, or about 90% to about 99%, or about 95% to about 99% by weight of one or more second segment monomers, (vi) the first segment reactive and the second segment are molecularly miscible (homogeneous) prior to curing or prior to crosslinking, as expressed by their properties in the state that are indicative of a monophasic polymer and (vii) at least one of the precursors and pre-adhesive composition is a homogeneous (single phase) polymer or a liquid polymer over a temperature range of 15°C to 200°C.

[0009] In another aspect, the acrylic block copolymer described above comprises two first reactive segments A of controlled molecular weight and position and a second segment B of controlled molecular weight and position, wherein the first reactive segments A are positioned on both sides sides of a second medium segment B in the polymer chain to define an ABA structure.

[0010] In yet another aspect, the acrylic block copolymer described above comprises two molecular weight and position controlled second segments B and a first reactive segment A of molecular weight and position controlled, wherein the two second segments B are positioned on both the middle sides of the first A reactive segment in the polymer chain to define a BAB structure.

[0011] In yet another aspect, the present invention provides a pre-adhesive comprising the precursor described above, wherein at least a portion of the functional groups of the acrylic block copolymer of said precursor include ethyl-unsaturated linkages.

[0012] In another aspect, the present invention provides a composition comprising the precursor described above and a monomer having an acrylating functional group in which at least one of the functional groups of the at least one acrylic block copolymer can undergo a post-functionalization reaction - polymerization with the acrylating functional group to make the at least one acrylic block copolymer crosslinkable upon exposure to actinic radiation.

[0013] In one aspect, the present invention provides a method for forming a curable pre-adhesive composition after exposure to actinic radiation. The method comprises providing the precursor described above. The method also comprises modifying at least a portion of the functional groups of the acrylic block copolymer of said precursor to form the preadhesive composition wherein the modification produces ethylically unsaturated bonds in the acrylic block copolymer which, upon exposure to actinic radiation, effects curing the pre-adhesive composition to thereby produce an adhesive composition.

[0014] In another aspect, the present invention provides pre-adhesive compositions produced by the observed method.

[0015] In yet another aspect, the present invention also provides a method for forming an adhesive composition comprising providing the precursor described above, said precursor comprising Acrylic Block Copolymer described above. At least a portion of the functional groups of said acrylic block copolymer include ethyl-unsaturated linkages. The method also comprises exposing the pre-adhesive composition to actinic radiation to thereby at least partially cure the pre-adhesive composition to form the adhesive composition.

[0016] In yet another aspect, the present invention provides adhesive compositions produced by the observed method.

[0017] How it will be realized, the object described in this document is capable of other and different modalities and its various details are capable of modifications in various aspects, all without departing from the claimed subject. Thus, drawings and description should be considered illustrative and not restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 is a schematic illustration depicting a conventional polymer including various reactive functional groups and upon exposure to UV radiation, formation of a conventional randomly crosslinked network.

[0019] Figure 2 is a schematic illustration depicting controlled architecture polymers (PACs) and upon exposure to UV radiation, formation of an enhanced end-linked network according to the present invention.

[0020] Figure 3 is a schematic illustration of a conventional randomly crosslinked network and, upon incorporation into an adhesive, typical adhesive properties associated with this network.

[0021] Figure 4 is a schematic illustration of an improved end-linked network and, upon incorporation into an adhesive, typical adhesive properties associated with that network in the adhesive according to the present invention.

[0022] Figure 5 is a schematic process diagram showing a representative process and system for producing an adhesive in accordance with the present invention.

[0023] Figure 6 is a schematic illustration of a tape article including an adhesive according to the present invention.

[0024] Figure 7 is a schematic cross-sectional view of another tape article in accordance with the present invention.

[0025] Figure 8 is a schematic cross-sectional view of another tape article in accordance with the present invention.

[0026] Figure 9 is a schematic cross-sectional view of another tape article in accordance with the present invention.

[0027] Figure 10 is a schematic cross-sectional view of another tape article in accordance with the present invention.

[0028] Figure 11 is a schematic cross-sectional view of a sealing or closure assembly including a region of an adhesive according to the present invention.

[0029] Figure 12 is a graph of melt viscosity versus temperature in example 1

[0030] Figure 13 is a graph of melt viscosity versus temperature in example 4

[0031] Figure 14 is a graph of melt viscosity versus temperature in example 17

[0032] Figure 15 is a graph of Tan (delta) versus temperature for samples 29-31 and commercial controls

[0033] Figure 16 is a graph of Modulus of elasticity/storage as a function of temperature for samples 29-31 and commercial controls

DETAILED DESCRIPTION OF MODALITIES

[0034] As used herein, terms such as "typically" are not intended to limit the scope of the claimed invention or to imply that certain features are critical, essential, or even important to the structure or function of the claimed invention. Rather, these terms are only intended to highlight alternative or additional features that may or may not be used in a particular embodiment of the present invention.

[0035] As used in this document, the terms "comprises(m)", "includes (in)", "has(em)", "has(ê)", "contains (ê)" and their variants, are transient open expressions, terms, or words that do not preclude the possibility of additional acts or structure.

[0036] As used herein, the term "polymer" may refer to a polymeric compound prepared by the polymerization of monomers, either of the same type or of a different type. The generic term "polymer" encompasses the terms "homopolymer", "copolymer" and the like.

[0037] As used herein, the term "molecularly miscible" means a compound or mixture of compounds that exhibit properties in the general state that can be observed and/or measured by one skilled in the art and are indicative of single-phase behavior or of a single phase polymer. The term "single-phase behavior" refers to uniform or substantially uniform behavior or physical properties. Regarding the acrylic copolymer, the observation of a single Tg is indicative of miscibility of the polymeric segment. The single Tg is intermediate between those of the constituent polymeric segments and varies between these values as the relative amounts of each segment are changed. In contrast to the single-phase behavior evidenced by a molecularly miscible compound or mixture of compounds, at a given temperature, a phase-separated compound demonstrates several independent sets of properties that are attributable to the different phases of matter present in it. These property sets include, without limitation, Tg, solubility parameters, refractive index, and physical state/phase of matter. Thus, the term "separate phase" is defined as two or more substances that are molecularly segregated due to one or more chemical and/or physical properties dependent on, without limitation, polarity, molecular weight, relative amounts of polymer segments and Tg (phase of the subject).

[0038] Evidence of immiscibility/incompatibility between blocks/segments of a block copolymer, such as an ABA block copolymer, can be confirmed through rheological measurements, such as Dynamic Mechanical Analysis (DMA) or Differential Scanning Calorimetry (DSC) and the microstructure determined from microscopy. Miscible polymers do not exhibit heterogeneity (ie, they are monophasic polymers) in their microstructure. The degree of miscibility/compatibility of a polymer blend can simply be determined by measuring the glass transition temperature(s) in a DMA or DSC. The presence of two Tgs indicates immiscibility, while the presence of only a single Tg indicates a miscible mixture. For block copolymers with mutually incompatible blocks, the microdomains formed by the different blocks exhibit different/different Tgs and for incompatible block copolymers separate Tg values are also observed in the DMA and/or DSC plots. For example, for typical styrenic and acrylic ABA block copolymers, hard A block and soft B block have sufficiently different solubility parameters that they are not thermodynamically compatible with each other. As a result, block copolymer-based adhesives have a unique microphase-separated morphology, in which the A-blocks form a hard phase embedded in a smooth continuous phase composed of B-blocks. Of the two types of blocks present in ABA block copolymers, block copolymers generally exhibit two distinct glass transitions (a bimodal DMA tan δ curve) at temperatures very close to those of the corresponding homopolymers. The presence of acid, however, in block copolymers such as P(MMA/MAA)-PBA-P(MMA/MAA) increases the final block Tg and also improves phase separation between the soft acrylate and hard PMMA domains. . Therefore, block copolymers can exhibit morphologies ranging from segregated materials in two phases to homogeneous materials in one phase.

[0039] The acrylic polymers contemplated by this document are architectural polymers formed through a controlled process of free radicals, including the selection of monomers that form copolymers in homogeneous (single-phase) acrylic blocks, as evidenced by the presence of a single Tg peak, indicative of a homogeneous (single-phase) polymer prior to crosslinking.

[0040] As used herein, the term "homogeneous polymer" is a block copolymer having substantially one morphological phase in the same state. For example, a block copolymer of two or more segments in which one segment is miscible with another segment is considered homogeneous in the liquid state. This morphology is determined using atomic force microscopy (AFM) or scanning electron microscopy (SEM). By miscible, it is meant that a block copolymer of two or more segments exhibits single-phase behavior for the glass transition temperature, for example, the Tg would exist as a single, sharp transition temperature in a tan δ trace of the mechanical dynamic thermal analyzer (DMTA) (the ratio of loss modulus to storage modulus) as a function of temperature. In contrast, two separate transition temperatures would be observed for an immiscible block copolymer, typically corresponding to the temperatures for each of the individual segments of the block copolymer. Thus, a block copolymer is miscible when there is a Tg indicated in the DMTA trace. A miscible block copolymer is homogeneous, while an immiscible block copolymer is heterogeneous.

[0041] In contrast, the term "heterogeneous polymer" means a block copolymer having two or more morphological phases in the same or different state. For example, a two-segment block copolymer in which one segment forms discrete packets dispersed in a matrix of another segment is considered heterogeneous. A heterogeneous polymer is also defined to include cocontinuous segments where the components of the block copolymer are visible separately, but it is not clear which is the continuous phase and which is the discontinuous phase. This morphology is determined using scanning electron microscopy (SEM) or atomic force microscopy (AFM). By continuous phase is meant the matrix phase in a heterogeneous block copolymer. By discontinuous phase is meant the dispersed phase in a heterogeneous block copolymer.

[0042] DMA was performed on a TA Instruments AR2000 rheometer equipped with parallel plate clamps. 1.0 mm thick samples were placed in the clamp and annealed at 70oC for 10 minutes to ensure good adhesion. Samples were then cooled to -60°C to initiate a temporary sweep to 150°C at an increment rate of 3°C/min. During the temperature increment, the samples were oscillated at a frequency of 10 rad/s.

[0043] Representative and non-limiting examples of glass transition temperature (Tg) ranges for the precursor, acrylic block copolymers and/or pressure sensitive adhesives of the present invention are from about 15°C to about -115° C, or from about 0°C to about -80°C and/or from about -35°C to about -60°C.

[0044] The present invention is based on work with controlled architecture polymers (CAPs) described in common property applications US 2011/0118372 A1, US 2013/0059971 A1 and US 2014/0329958 A1, the content of which is incorporated by this document by reference in its entirety. Additional details of the controlled architecture polymers, including their syntheses, are described in the noted common property patent applications.

[0045] The present invention relates to the formation of adhesives that can be activated or cross-linked upon exposure to actinic radiation. Adhesives include architecturally controlled polymers (referred to as "CAPs" or acrylic block copolymers) that include one or more functional groups along the backbone of the polymer that, upon such exposure, effect crosslinking or other activation. The terms "CAPs" and "acrylic block copolymer" are used interchangeably throughout this document. The present invention also relates to adhesives, including those CAPs with the mentioned functional groups. The present invention also relates to articles containing adhesives prepared by the methods described herein. Furthermore, the present invention relates to equipment and systems for preparing and/or processing adhesives and pre-adhesives.

[0046] Before turning attention to the details of the present invention and the numerous embodiments thereof, it is instructive to consider various terms and their definitions as used throughout the present document. The terms "polymerize" or "polymerization" refer to a process of reacting monomers together in a chemical reaction to form polymer. And the terms "reticular" or "reticulation" refer to a process of formation of bonds that connect a polymeric chain to another polymeric chain. The bonds can be covalent bonds or ionic bonds. The term "crosslink" can refer to the binding itself. The terms "heal" and "cure" refer to the terms "reticular" or "crosslink" and are used interchangeably.

[0047] In many embodiments of the present method invention, by modifying functional groups of polymers and crosslinking certain compositions, and particularly those that include CAPs, the resulting adhesives exhibit improved adhesive properties such as relatively high peel strength and shear strength . These improved adhesive properties are believed to result at least partially from (i) the majority of crosslinking involving functional groups of the polymers located at or near the terminal ends of the polymer chains and (ii) the absence or only a minor amount of crosslinking involving functional groups of the polymers located at or near the terminal ends of polymer chains. functional(s) located in the interior regions of the polymeric chains. The crosslinked network that results from the methods described herein is referred to herein as an "enhanced terminally connected network" or ETLN. As described in more detail in this document, forming an ETLN allows for lower adhesive coat weights, lower viscosities, and improved adhesive performance, among many other advantages and benefits. These and other aspects of the methods, CAP-based adhesives and ETLNs, and related articles are described in more detail throughout this document.

[0048] While in many embodiments, the methods of the present invention utilize adhesives including CAPs, it will be appreciated that the present invention also includes methods of modifying and crosslinking non-CAP-based adhesives. These and other aspects of the methods, non-CAP based adhesives modified and crosslinked by these methods, and related articles are described in more detail herein.

[0049] In general, the present invention provides a composition comprising, consisting essentially of, or consisting of a precursor and a reacting agent. The precursor comprising at least one acrylic block copolymer (also referred to as CAPs), the at least one acrylic block copolymer comprising (i) a first molecular weight and position controlled reactive segment comprising at least one monomer with a selected functional group from the group consisting of a self-reactive functional group, a reactive functional group, a non-reactive functional group and combinations thereof, and (ii) a second molecular weight and position controlled segment that includes at least one monomer with a functional group selected from the group consisting of a reactive functional group, a non-reactive functional group and combinations thereof. The reactive functionalities in the first reactive segment and the second segment can be the same or different from each other. The non-reactive functionalities in the first reactive segment and the second segment can be the same or different from each other. At least one of the functional groups of the at least one acrylic block copolymer may undergo a post-polymerization functionalization reaction with the reaction agent to make the at least one acrylic block copolymer crosslinkable upon exposure to actinic radiation. The at least one acrylic block copolymer is not crosslinkable after exposure to actinic radiation prior to the postpolymerization functionalization reaction. Notably, (i) the at least one acrylic block copolymer does not contain ethyl unsaturation along the polymer backbone and/or pendant groups, (ii) the reacting agent comprises at least one of a double bond and a functional group, being the functional group capable of reacting with at least one of the functional groups of the at least one acrylic block copolymer, (iii) the post-polymerization functionalization reaction is an acrylation reaction, and (iv) the post-polymerization functionalization reaction produces an ethyl unsaturated bond in the at least one acrylic block copolymer, the ethyl unsaturated bond being a double bond. The precursor forms a pre-adhesive composition after the post-polymerization functionalization reaction of the at least one acrylic block copolymer, and said pre-adhesive is at least partially cross-linkable upon exposure to actinic radiation to form an adhesive. The adhesive formed may be pressure sensitive adhesive. Actinic radiation is at least one of UV radiation and electron beam radiation.

[0050] The first reactive segment and the second segment are defined by (i) the type of monomers (that is, self-reactive, reactive and non-reactive monomers) present in the specific segment and (ii) the ratio of non-reactive monomers in each segment. The precursor disclosed herein comprises, consists essentially of, or consists of, among other features, a triblock acrylic copolymer having a structure {(A) (B) (C)} - {(B) (C)} - { (C) ( B) (A)} or a structure {(A) (B) (C)} - {(C)} - {(C) (B) (A)} or a structure {(A) ( C)} - {(C)} - {(C) (A)} structure, or a {(B) (C)} - {(C)} - {(C) (B)} structure, where A represents at least one monomer with a self-reactive functional group, B represents at least one monomer with a reactive functional group, and C represents at least one monomer with a non-reactive functional group. And {(A) (B) (C)}, {(A) (C)} and {(B) (C)} represent the first reactive segment while {(B) (C)} and { (C)} represent the second segment. That is, the first reactive segment(s) comprises or consists of a monomer having a self-reactive functional group, a monomer having a reactive monomer and a non-reactive monomer, or the first reactive segment(s) ) comprises or consists of a monomer with a self-reactive functional group and a monomer with a non-reactive functional group or the first reactive segment(s) comprises or consists of a monomer with a reactive functional group and a monomer with a non-reactive functional group, while the second reactive segment comprises or consists of a monomer with a reactive functional group and a monomer with a non-reactive functional group or the second reactive segment comprises or consists of only one monomer with a reactive functional group functional non-reactive. The at least one monomer having a reactive functional group in the first reactive segment and the at least one monomer having a reactive functional group in the second segment may be the same type of monomer(s) or different type of monomer(s). monomer having a non-reactive functional group on the first reactive segment and the at least one monomer having a non-reactive functional group on the second segment may be the same type of monomer(s) or different type of monomer(s) The first segment(s) reactive(s) includes about 40% to about 99%, or about 45% to about 99%, or about 50% to about 99%, or about 55% to about 99% , or about 60% to about 99%, or about 65% to about 99%, or about 70% to about 99%, or about 75% to about 99%, or about 80% to about 99%, or about 85% to about 99%, or about 90% to about 99%, or about 95% to about 99% by weight of one or more unreactive monomers. The first reactive segment(s) comprises about 40% to about 99%, or about 45% to about 99%, or about 50% to about 99%, or about 55 % to about 99%, or about 60% to about 99%, or about 65% to about 99%, or about 70% to about 99%, or about 75% to about 99% , or about 80% to about 99%, or about 85% to about 99%, or about 90% to about 99%, or about 95% to about 99% by weight of one or more monomers of the second reactive segment.

[0051] The precursor described by this document comprises, consists essentially of, or consists of, among other features, a diblock acrylic copolymer with a structure {(A) (B) (C)} - {(B) (C) } or a structure {(A) (C)} - {(C)}, or a structure {(B) (C)} - {(C)}, where A represents at least one monomer with an auto functional group reactive, B represents the at least one monomer with a reactive functional group and C represents the at least one monomer with a non-reactive functional group. And {(A) (B) (C)} and {(A) (C)} and {(B) (C)} represent the first reactive segment while {(B) (C)} and { (C)} represent the second segment. That is, the first reactive segment(s) comprises or consists of a monomer with a self-reactive functional group, a monomer with a reactive functional group, and a monomer with a non-reactive functional group or the first segment(s) ( s) reactive(s) comprises or consists of a monomer with a self-reactive functional group and a monomer with a non-reactive functional group or the first reactive segment(s) comprises or consists of a monomer with a reactive functional group and a monomer with a non-reactive functional group, while the second segment comprises or consists of a monomer with a reactive functional group and a monomer with a non-reactive functional group or the second segment comprises or consists of only one monomer with a non-reactive functional group. The at least one monomer having a reactive functional group in the first reactive segment and the at least one monomer having a reactive functional group in the second segment may be the same type of monomer(s) or different type of monomer(s). monomer having a non-reactive functional group on the first reactive segment and the at least one monomer having a non-reactive functional group on the second segment may be the same type of monomer(s) or different type of monomer(s) The first segment(s) reactive(s) includes about 40% to about 99%, or about 45% to about 99%, or about 50% to about 99%, or about 55% to about 99% , or about 60% to about 99%, or about 65% to about 99%, or about 70% to about 99%, or about 75% to about 99%, or about 80% to about 99%, or about 85% to about 99%, or about 90% to about 99%, or about 95% to about 99% by weight of one or more unreactive monomers. The first reactive segment(s) includes about 40% to about 99%, or about 45% to about 99%, or about 50% to about 99%, or about 55 % to about 99%, or about 60% to about 99%, or about 65% to about 99%, or about 70% to about 99%, or about 75% to about 99% , or about 80% to about 99%, or about 85% to about 99%, or about 90% to about 99%, or about 95% to about 99% by weight of one or more second segment monomers. The term "reactive functional group" refers to a functional group that is capable of reacting with another functional group. The term "self-reactive functional group" refers to a functional group that is capable of reacting with (i) a second identical self-reactive functional group, (ii) a different second self-reactive functional group, and/or (iii) a reactive functional group. That is, the self-reactive functional group can react with another identical self-reactive functional group, with another different self-reactive functional group and/or with a reactive functional group. Self-reactive functional groups are able to polymerize with themselves. Non-limiting examples of self-reactive functional group are selected from the group consisting of silyl, silane, anhydride, epoxy, alkoxymethylol, cyclic ethers, acetoacetyl groups, isocyanate, cyclic esters and mercapto (thiol). Non-limiting examples of the reactive functional group are selected from the group consisting of hydroxyl, carboxyl, carbonyl, carbonate ester, isocyanate, epoxy, vinyl, amine, amide, imide, anhydride, mercapto (thiol), acid, acrylamide, acetoacetyl groups alkoxymethylol, cyclic ether groups and combinations thereof.

Controlled architecture polymers (CAPs)

[0052] In particular embodiments, the actinic radiation-curable and cross-linkable adhesives of the present invention are produced from architecture-controlled polymers. In many embodiments, the polymers are acrylic polymers.

[0053] In many embodiments of the present invention, the actinic radiation-curable and crosslinkable adhesives that include architecturally controlled polymers have one or more reactive functional groups incorporated into selected blocks or regions of the polymer in designated concentrations in those regions. As noted, in many embodiments, the polymers are acrylic polymers.

[0054] The polymerizable monomers and comonomers contemplated by this document may include as reactive functional groups acrylonitrile groups, acrylamide groups, methacrylamide groups, vinyl ester groups, vinyl ether groups, vinyl amide groups, vinyl ketone groups, styrene groups, halogen-containing groups, ionic groups, acid containing groups, base containing groups, olefin groups, silane groups, epoxy groups, hydroxyl groups, anhydride groups and mixtures of two or more groups thereof. It is also contemplated to include silyl groups, carboxyl groups, carbonyl groups, carbonate ester groups, isocyanate groups, amine groups, amide groups, imide groups, mercapto groups and acetoacetyl groups in any combination and/or in combination with one or more of any of the previously observed groups.

[0055] Acrylonitrile groups may include acrylonitrile and alkyl-substituted acrylonitriles. Alkyl groups typically contain from 1 to about 20 carbon atoms, and in one embodiment from 1 to about 10 carbon atoms and in another embodiment from 1 to about 5 carbon atoms. Examples include methacrylonitrile and ethacrylonitrile.

[0056] Acrylamide groups may include acrylamide and its derivatives, including N-substituted alkyl and aryl derivatives thereof. These include N-methyl acrylamide, N,N-dimethyl acrylamide, t-octyl acrylamide, N-aminoethyl acrylate, N-aminoethyl methacrylate and the like.

[0057] Methacrylamide groups may include methacrylamide and its derivatives, including N-substituted alkyl and aryl derivatives thereof.

[0058] Vinyl ester groups may include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl versitate, vinyl isobutyrate and the like.

[0059] Vinyl ether groups can include vinyl ethers having 1 to about 8 carbon atoms, including ethyl vinyl ether, butyl vinyl ether, 2-ethyl hexyyl vinyl ether and the like.

[0060] Vinyl amide groups can include vinyl amides having 1 to about 8 carbon atoms, including vinyl pyrrolidone and the like.

[0061] Vinyl ketone groups can include vinyl ketones having 1 to about 8 carbon atoms, including ethyl vinyl ketone, butyl vinyl ketone and the like.

[0062] Styrene groups may include styrene, indene and substituted styrenes represented by formula (I): wherein each of A, B, C, D, E and F is independently selected from hydrogen, C1 to about C4 alkyl or alkoxy groups (especially methyl or methoxy groups), halogroups (especially chlorine), thio, cyano , carboxylic acid or ester, or fluorinated alkyl groups of 1 to about 4 carbon atoms. Examples include methyl styrene (sometimes called vinyl toluene), alpha-methyl styrene, divinylbenzene, chlorostylene, chloromethyl styrene, and the like.

[0063] Halogen-containing groups may include vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene bromide, vinylidene fluoride, halogen-substituted propylene monomers and the like, with vinyl bromide and chloride being preferred of vinylidene.

[0064] Ionic groups may include sodium vinyl sulfonate, sodium styrene sulfonate, sodium methyl sulfonate, sodium acrylate, sodium methacrylate and the like, with sodium vinyl sulfonate, sodium sulfonate, sodium styrene sulfonate being preferred sodium and sodium methylyl sulfonate.

[0065] Acid-containing groups may include unsaturated carboxylic acids containing from 3 to about 20 carbon atoms. Preferred groups include acrylic acid, methacrylic acid, vinylsulfonic acid, itaconic acid, beta carboxy ethyl acrylate, mono-2-acroyloxypropyl succinate and the like.

[0066] Base-containing groups may include vinyl pyridine and the like.

[0067] Olefin groups may include isoprene, butadiene, straight and branched chain C2 to C8 alpha-olefins such as ethylene, propylene, butylene, isobutylene, diisobutylene, 4-methyl pentene-1, 1-butene, 1-hexene , 1-octene and the like.

[0068] Silane groups may include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldipropoxysilane, Y-methacryloxypropyltrimethoxysilane, Y-methacryloxypropyltriethoxysilane, Y-methacryloxypropyltripropoxysilane, Y-methacryloxydimethoxysilane, Y-methacryloxypropyl - methyldimethoxysilane, Y-methacryloxypropylmethyldiethoxysilane, Y-methacryloxypropylmethyldipropoxysilane, Y-methacryloxymethyldimethoxysilane, Y-methacryloxymethyltrimethoxysilane, Y-methacryloxymethyltriethoxysilane, (methacryloxymethyl)methyldimethoxysilane, (methacryloxymethyl)-methyldiethoxysilane, Y-methacryloxypropyltriacetoxysilane, Y-acryloxypropyltrimethoxysilane, Y-acryloxypropyl triethoxysilane , Y—methacryl—oxymethyldiethoxysilane, Y—acryloxypropyltripropoxysilane, Y—acryloxypropyl—methyldimethoxysilane, Y—acryloxypropylmethyldiethoxysilane, Y—acryloxypropiomethyl—oxy—ethane and others.

[0069] Epoxy groups may include, for example, glycidyl methacrylate and glycidyl acrylate.

[0070] The hydroxyl groups may include, for example, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyl isopropyl acrylates, hydroxyl isopropyl acrylates, hydroxyl isopropyl methacrylate, hydroxyl butyl acrylate, hydroxyl butyl methacrylate and the like.

[0071] The anhydride groups may include, for example, maleic anhydride, itaconic anhydride, citraconic anhydride and the like.

[0072] In addition to the monomer with functional group(s), the reactive segment may include at least one monomer with formula (II): wherein R3 is H or CH3 and R4 is a straight or branched chain, saturated alkyl group having from 4 to 14 carbon atoms. The reactive segment may include, instead or additionally, at least one monomer with formula (III): wherein R is H or CH3 and X represents or contains a functional group capable of cross-linking.

[0073] Representative preferred reactive functional groups incorporated into the polymers described herein include, but are not limited to, acrylic acid, 2-methacryloxyethylphthalic acid (PAMA) and combinations thereof. It will be appreciated that a wide variety of other reactive functional groups can be used instead of or in conjunction with any of these reactive functional groups.

[0074] As noted above, after crosslinking the present adhesives of the present invention and forming an improved terminally bonded polymeric network, the resulting improved adhesive exhibits certain properties that are at least comparable to, and in many cases superior to, those of adhesives that use conventional random crosslinking polymeric networks. Figure 1 is a schematic illustration depicting a conventional polymer including various reactive functional groups and upon exposure to UV radiation, formation of a conventional randomly crosslinked network. In Figure 1, the various functional groups are schematically represented by the vertical line segments located along the polymer chain or backbone represented by the horizontal line segment. After crosslinking, crosslinking involves interior regions of the polymers as a result of many functional groups located in these interior regions. Figure 2 is a schematic illustration depicting controlled architecture polymers (PACs) and upon exposure to UV radiation, formation of an enhanced end-linked network in accordance with the present invention. CAPs include several functional groups located mainly at the terminal or near ends of polymers. Thus, after crosslinking, the network that forms is characterized by crosslinking bonds primarily at the terminal ends of the polymers, and an absence or relatively minor extent of crosslinking involving interior regions of the polymers.

[0075] The resulting polymeric networks influence and, in many ways, determine the physical properties of the resulting adhesives. Figure 3 is a schematic illustration of a conventional randomly crosslinked network and, upon incorporation into an adhesive, typical adhesive properties associated with that network. Figure 4 is a schematic illustration of an improved end-linked network and, upon incorporation into an adhesive, typical adhesive properties associated with that network in the adhesive according to the present invention. While the graphs in Figures 3 and 4 do not contain values on the y-axis, each graph is displayed with the same scale. Thus, the network polymer created through controlled architectural polymerization and depicted in Figure 4 demonstrates improved peel strength (pounds per linear inch) and shear strength (minutes) when compared to the randomly crosslinked network depicted in Figure 3.

No CAPs

[0076] In certain embodiments, the actinic radiation-curable and cross-linkable adhesives of the present invention are produced from polymers that are not architecturally controlled polymers or as referred to herein as "non-PACs". These adhesives are free or substantially free of controlled architecture polymers.

[0077] In many applications involving non-CAP based adhesives, the polymers are acrylic polymers or alkyl acrylates.

[0078] The alkyl acrylates and alkyl methacrylates used in the present invention include straight chain alkyl groups, branched chain alkyl groups, or cyclic alkyl groups, and in many embodiments contain from 1 to about 24 carbon atoms. In particular embodiments, the alkyl group contains from 1 to about 12 carbon atoms.

[0079] In a particular embodiment, the alkyl acrylate or alkyl methacrylate monomers have from about 4 to about 8 carbon atoms. Such monomers are generally available commercially as commodity chemicals and are less expensive than the longer chain alkyl acrylates and methacrylates. They also tend to produce copolymers with a good balance of stickiness and flaking.

[0080] A representative, but not limiting, list of alkyl acrylates and alkyl methacrylates useful in the practice of the present invention includes methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, isohexyl acrylate, cyclohexyl acrylate, iso-octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, stearyl acrylate, isobornyl acrylate and mixtures thereof, as well as analogous methacrylate monomers. It should be appreciated, however, that alkyl methacrylates generally produce copolymers with higher Tg than their alkyl acrylate counterparts. Therefore, when alkyl methacrylates are used, they are used only in small amounts. As a general rule, alkyl methacrylates comprise no more than about 15% of the total weight of all monomers.

[0081] The non-CAP polymer(s) includes one or more reactive functional groups, as described herein, in association with the CAPs. However, the one or more reactive functional groups can be present along the polymeric chain or in the backbone in an unstructured, random or non-ordered manner.

[0082] Representative, non-limiting examples of glass transition temperature (Tg) ranges for non-CAP polymers generally range from -60°C to about -35°C. However, it will be appreciated that polymers of the present invention can exhibit Tg outside this range, such as less than -60°C and/or greater than -35°C.

[0083] It is also contemplated that the present invention may include combinations or mixtures of CAPs and non-PACs.

Pre-stickers and adhesives

[0084] After modifying the functional groups on the polymers to make the groups activatable by actinic radiation and more particularly activatable by UV, the polymers can be incorporated into adhesive and/or pre-adhesive compositions.

[0085] As previously noted, the present invention provides pre-adhesive compositions that, after activation, undergo cross-linking to produce an adhesive with particular properties and/or characteristics. In many embodiments, pre-adhesive compositions include PACs which, upon activation, undergo cross-linking to produce an adhesive having certain properties and/or characteristics.

[0086] More specifically, in many embodiments, the cross-linkable and radiation-activatable adhesives include architecture controlled polymers or CAPs. In many embodiments of the present invention, the CAPs are those described in one or more pending applications owned by the Applicant, which include US 2011/0118372; US 2013/0059971; and US 2014/0329958. Details of polymers of particular embodiments are provided in this document. However, it will be understood that the present invention includes the use of any of the polymers described in these applications.

[0087] In certain embodiments, at least one of the precursors and pre-adhesives described above exhibit a viscosity within a range of 1,000 cps (1Pa.s) to 80,000 cps (80Pa.s) at a temperature in the range of 110° C to 180°C. In particular embodiments, at least one of the precursors and the pre-adhesive exhibits a viscosity within a range of 30,000 cps (30Pa.s) to 40,000 cps (40Pa.s) at a temperature within a range of 120°C to 140°C. °C. In other embodiments, at least one of the precursors and the pre-adhesive exhibits a viscosity within a range of 40,000 cps (40Pa.s) to 50,000 cps (50Pa.s) at a temperature within a range of 120°C to 140°C. °C. And, in still other embodiments, at least one of the precursor and preadhesive exhibits a viscosity in the range of 1,000 cps (1Pa.s) to 15,000 cps (15Pa.s) at a temperature in the range of 110°C to 130° W.

[0088] It will be understood that the present invention is in no way limited to adhesives or pre-adhesives exhibiting these particular viscosities. It is contemplated that the present invention may also include at least one of precursors and pre-adhesives exhibiting such viscosities at temperatures below 110°C and/or at temperatures above 180°C. Furthermore, it is contemplated that the present invention may also provide at least one of precursors and preadhesives that exhibit viscosities less than 1000 cps (1Pa.s) and/or greater than 80,000 cps (80Pa.s) over a wide range. of temperatures.

[0089] In certain embodiments, the adhesives and/or pre-adhesive compositions of the present invention may comprise one or more actinic radiation initiators. While not wishing to be bound by any particular theory, it is believed that, in many embodiments of the present invention, the initiator(s), when irradiated with actinic radiation and particularly UV light, are excited to a higher energy state. high and abstract a hydrogen atom from a functional group on the polymer, thereby generating a free radical that is available for further reaction, such as free radical addition crosslinking with another polymer chain or functional group on the polymer. However, it will be understood that the present invention includes the use of almost any type of initiator and is not limited to those that abstract hydrogen atoms. For example, a variety of initiators are known to decompose or split into free radicals upon exposure to light, and more particularly to UV radiation.

[0090] A variety of initiators are known and can potentially be incorporated into the present invention of adhesives and pre-adhesives, including benzophenone, acetophenone, acyl phosphine, thioxanthone, derivatives of these compounds, and similar compounds. Each compound functions as a photoinitiator, absorbing energy in the UV region of the electromagnetic spectrum.

[0091] Several types of photoinitiators are known that absorb in the near UV region of the spectrum, including acylphosphine oxide-type photoinitiators, benzophenone-type photoinitiators with red shift, and thioxanthone-type photoinitiators. Many of these may be suitable for use with the present compositions of the present invention.

[0092] Commercially available acylphosphine oxide-type photoinitiators include "Lucirin TPO" (2,4,6-trimethylbenzoyldiphenylphosphine oxide) and "Lucirin TPO-L" (liquid), sold by BASF, and "BAPO" (Acylphosphine oxide). bis 2,6-dimethoxybenzoyl-2,4-trimethylpentylphosphine), sold by Ciba.

[0093] So-called "redshifted benzophenone-type photoinitiators" are derivatives of benzophenone in which one or more hydrogen atoms are replaced by a functional group or groups that cause a redshift (towards wavelengths longer) in the UV absorption spectrum of the molecule compared to the UV absorption spectrum of benzophenone. An example is "QUANTACURE BMS" (4-benzoyl-4'-methyldiphenylsulfide).

[0094] Commercially available thioxanthone-type photoinitiators include "Quantacure ITX", which is believed to be a mixture of 2-isopropyl and 4-isopropylthioxanthone isomers.

[0095] Other suitable photoinitiators can be identified by those skilled in the art and used in the present invention. Additionally, if the adhesive is pigment-free composite, photoinitiators that absorb at shorter UV wavelengths can be employed, including cheaper and simpler photoinitiators such as unsubstituted acetophenone, benzyl, benzophenone, quinone, and thioxanthone.

[0096] The total amount of initiators added to the polymer in the preparation of the adhesive or pre-adhesive depends on several factors, including the amount of pigment and/or other agents added, the layer weight (thickness) of the adhesive on the substrate, the speed of the band during healing and the type and cost of primers used. In many embodiments, the primer is the most expensive ingredient in the adhesive. Therefore, it is usually desirable to minimize the amount of initiator added to the polymer, provided that sufficient initiator is included to achieve the desired final properties of the resulting composition.

[0097] In certain embodiments of the present invention, a pigment or other coloring agent is added to the composition, typically prior to crosslinking, in order to make the adhesive opaque and/or impart color to the adhesive. Opaque pigments, such as titanium dioxide, are typically added by the coatings industry precisely because of their high hiding power. However, their presence generally interferes with the UV-initiated crosslinking of the adhesive polymer. In the present invention, however, initiators that absorb in the near UV region of the spectrum can be employed with pigmented (as well as unpigmented) formulations, thereby avoiding interference with the UV-initiated crosslinking of the adhesive.

[0098] The amount of pigment added to the composite polymer in a given formulation, such as the amount of initiator, depends on several factors, including the desired degree of opacity, the desired degree of curing, whether other fillers are present, the type and amount of photoinitiator present and cost considerations.

[0099] For the present invention, where pigmented adhesive or pre-adhesive compositions are used, UV-initiated crosslinking can be facilitated by decreasing the amount of titanium dioxide present (or other pigment) and/or increasing the amount of initiator. However, in practice, pigment loadings above about 15 parts pigment per hundred parts polymer (or, if the copolymer is adhered, about 15 parts pigment per 100 parts more adherent polymer) are less preferred than lower pigment loads. Cross-linked, UV-initiated pressure-sensitive adhesive compositions having high cohesive strength can be prepared in accordance with the present invention with higher pigment loadings, but require higher (and more expensive) initiator concentrations and/or crosslinking times. longer.

[00100] In some embodiments, the adhesive or pre-adhesive composition is formulated with a colored (not white) pigment.

[00101] In general, yellow and red pigments do not substantially interfere with photoinitiators that absorb in the UV region. Therefore, adhesives composed with these pigments can be UV cross-linked to high cohesive strength using UV-activatable photoinitiators. Blue pigments tend to absorb strongly in at least part of the near UV region. By minimizing the amount of blue pigment that is added, however, UV crosslinked adhesives can be prepared in the manner described herein.

[00102] In addition to the pigment and the primer(s), in some embodiments, the adhesive or pre-adhesive is further compounded with an adhesive. In certain embodiments, such as if the adhesive is a pressure sensitive adhesive, an adhesive may be added to improve the adhesion of the pressure sensitive adhesive.

[00103] A variety of adhesives, many of which are well known in the industry, can potentially be used in the practice of the present invention. Representative and non-limiting examples of such tackifiers include hydrocarbon resins and rosin resins. Such tackifiers include, but are not limited to, rosin and rosin derivatives, including rosin materials naturally occurring in pine oleoresin, as well as derivatives thereof, including rosin esters, modified rosin such as fractionated, hydrogenated, dehydrogenated, and polymerized rosin, modified resin esters and the like. Generally, up to about 45 parts of tackifiers per hundred parts of polymer are added. However, it will be appreciated that the present invention includes the use of smaller amounts and/or larger amounts of adhesives.

[00104] A wide variety of adhesives are commercially available, including, but not limited to, Foral® 85 (glycerol ester of a highly stabilized resin), Foral® 105 (pentaerythritol ester of a hydrogenated resin), stabilization ester 10 and Pentalyn® H, manufactured and sold by Hercules, Inc., PE Estergum and the like, manufactured by Arizona Chemical Co., and Sylvatac® 40N, Sylvatac® RX, Sylvatac® 95 and the like, manufactured by Sylvachem Corporation.

[00105] They can also be used as adhesive terpenes, which are hydrocarbons of the formula C10H16, which occur in most essential oils and oleoresins of plants, and terpene resins modified with phenol, such as alpha pinene, beta pinene, dipene, limonene, myrecene, bornylene , camphene and the like. Various aliphatic hydrocarbon resins such as Escorez™ 1304, manufactured by Exxon Chemical Co., and aromatic hydrocarbon resins based on C9, C5, dicyclopentadiene, coumaron, indene, styrene, styrenes and substituted styrene derivatives and the like may also be used.

[00106] Hydrogenated and partially hydrogenated resins, such as Regalrez™ 1018, Regalrez™ 1033, Regalrez™ 1078, Regalrez™ 1094, Regalrez™ 1126, Regalrez™ 3102, Regalrez™ 6108, etc., produced by Hercules Corporation, can be used as stickers in the current affairs as well. Various terpene phenolic resins of the type SP 560, manufactured and sold by Schenectady Chemical Inc., Nirez 1100, manufactured and sold by Reichold Chemical Inc., and Piccolyte® S-100, manufactured and sold by Hercules Corporation, are particularly useful adhesives in the present invention. In addition, various blended aliphatic and aromatic resins, such as Hercotex AD 1100, manufactured and sold by Hercules Corporation, can also be used as adhesives.

[00107] Furthermore, the actinic radiation-curable and cross-linkable adhesive compositions may comprise one or more inhibitors. A viable free radical scavenger may be present to prevent premature gelling either in storage or in coating preparation, especially in the case of hot melt adhesive compositions. Inhibitors comprising phenolic compounds are one class of such materials that can be used in the present invention, including, for example, 4-methoxyphenol (MEHQ, hydroquinone methyl ether), hydroquinone, 2-methylhydroquinone, 2-t-butyl- hydroquinone, t-butyl catechol, butylated hydroxytoluene and butylated hydroxy anisole and the like and combinations thereof. Other inhibitors that may be used include phenothiazine and anaerobic inhibitors such as NPAL (tris-(N-nitroso-N-phenylhydroxylamine) aluminum salt) type inhibitors from Albemarle Corporation, Baton Rouge, La. Combinations of inhibitors can be used.

[00108] The adhesives or pre-adhesives of the present invention may further comprise one or more conventional adjuvants, such as fillers, plasticizers, diluents and the like. Combinations of one or more of these components may be used, including combinations with pigment(s) and/or adhesive(s). If desired, diluents such as plasticizers can be added in place of a portion of the tackifier in order to alter the tack and cohesive strength properties.

[00109] In general, actinic radiation-curable and crosslinkable adhesives include at least 95% solids, in many embodiments at least 98% solids, in particular embodiments at least 99% solids, and in certain versions at least 99% solids. .5% solids.

[00110] In many embodiments, the adhesives are in the form of melt processable or hot melt adhesives, as known in the art. These adhesives are free or substantially free of solvents.

[00111] In many embodiments of the present invention, the adhesives are in the form of pressure sensitive adhesives. A description of pressure sensitive adhesives and their characteristics can be found in Encyclopedia of Polymer Science and Engineering, vol. 13) Wiley-Interscience Publishers (New York, 1988). Further description of pressure sensitive adhesives and their characteristics can be found in Encyclopedia of Polymer Science and Technology, vol. 1, Interscience Publishers (New York, 1964).

Methods

[00112] The present invention also provides methods of modifying functional groups located along a polymer backbone into groups activatable by actinic radiation and more particularly activatable by UV. Methods generally comprise providing architecturally controlled polymers with one or more functional groups located along a polymer backbone. The methods also comprise modifying at least a portion of the functional groups to produce ethyl-unsaturated linkages which, upon exposure to actinic radiation, effect cure of the pre-adhesive composition to thereby produce an adhesive composition.

[00113] The observed modification can occur by one or more steps or operations in which the functional groups react with one or more reagents to produce the ethylically unsaturated bonds.

[00114] The present invention also provides methods for forming an adhesive composition. The methods involve providing a pre-adhesive composition including architecturally controlled polymers having one or more functional groups located along a backbone of the polymer. At least a portion of the functional groups include ethyl-unsaturated linkages. The methods also involve exposing the pre-adhesive composition to actinic radiation to thereby at least partially cure the pre-adhesive composition and form the adhesive.

[00115] The adhesives or compositions of the present invention are cured and/or crosslinked by exposure to actinic radiation, and particularly ultraviolet (UV) radiation or near UV radiation. Electron beam radiation can also be used. As will be appreciated, sufficient exposure to this radiation causes curing and/or crosslinking involving various functional groups incorporated into polymers and certain embodiments of CAPs.

[00116] The use of the aspects described by the present documents allows the formation of a pre-adhesive or adhesive formulation that can be further processed by subsequent or additional exposure to actinic radiation and particularly to UV radiation. Thus, an initial batch or desired amount of pre-adhesive or adhesive can be crosslinked or at least partially crosslinked in bulk and then stored or held for later application or coating onto a substrate of interest.

[00117] After the adhesive is coated onto a substrate with a desired coating weight, the coated substrate is irradiated with actinic radiation and particularly UV radiation to produce a crosslinked adhesive and, in many embodiments, a pressure sensitive adhesive with high strength cohesive at room temperature and elevated temperatures. A variety of UV light sources are known, including low, high and medium pressure mercury lamps, which emit in a wide range of wavelengths. Most pigmented and non-pigmented adhesives can be easily cured using a medium pressure mercury lamp, which has emission ranges ranging from 240 to 410 nanometers. Alternatively, UV sources that emit in a narrower range of wavelengths can be used, if desired, as long as the emission spectrum of the source overlaps with the absorption spectrum of functional groups modified with linkages and/or ethyl unsaturated initiators within of the sticker.

[00118] Figure 5 is a schematic process diagram depicting a representative process and system 10 for producing an adhesive and curing and crosslinking the adhesive in accordance with the present invention. System 10 generally comprises a dispenser or heater 12 for introducing one or more polymers and/or other components via feed line 14 to a reactor, mixer or mixer 22. Polymers are typically PACs and include one or more functional groups along the polymer chain, as described herein. Also provided are additional feed lines 16, 18 and 20 which can be used to selectively meter the desired amounts of reagent(s), initiator(s) and auxiliary components or other additives to the reactor/mixer 22.

[00119] After the reaction between the functional groups located along the polymer chain with reagent to form groups activatable by actinic radiation and, more particularly, activatable by UV, the resulting pre-adhesive is directed through line 24.

[00120] The adhesive on line 24 can be directly deposited or applied to one or more substrates on a moving web 42 (typically driven by the rotating cylinder 40) via line 34 or directed via line 36 to a storage unit 44 for further processing and/or subsequent application.

[00121] After deposition of the adhesive shown in Figure 5 as regions 46, the adhesive normally on the mobile network 42 is irradiated by an actinic radiation source, such as a UV emitter in stage 50 that directs UV rays 51 on regions 46 to crosslink the adhesive. Crosslinked adhesive results.

[00122] In particular embodiments, one or more conventional medium pressure mercury lamps can be used having spectral emissions from about 240 to about 410 nanometers, and light intensities from about 5 to 10 kWatts/m2 . Non-limiting examples of UV light intensities for processing adhesives of the present invention can range from about 0.1 to about 100 kWatts/m2, in certain embodiments from 1 to 50 kWatts/m2, and in particular embodiments from 1 to 20 kWatts/m2. The coated substrate is conveyed on a moving net under or near the source of UV radiation, where the net temperature can range from 45°C to 125°C. The dosage of UV radiation received by the coated adhesive film is controlled by adjusting the UV lamp intensity and/or grid speed. Non-limiting examples of time periods for processing adhesives of the present invention are typically less than 60 minutes, typically less than 10 minutes, in many embodiments less than 1 minute, and in specific embodiments less than 10 seconds.

[00123] When exposing the adhesive to observed conditions, if the adhesive includes CAPs, the adhesive will include an ETLN. As described earlier, the ETLN adhesives of the present invention exhibit a variety of advantages and benefits, particularly when compared to uncontrolled architecture polymers that produce randomly crosslinked networks.

[00124] As will be appreciated, during the conversion of the composition(s) of the present invention from a pre-adhesive to a pressure sensitive adhesive, in many embodiments, the modulus of the composition changes as the glass transition temperature (Tg ) does not change or remain substantially the same.

Articles

[00125] The present invention provides a wide variety of articles that include the mentioned compositions, pre-adhesives and/or adhesives. Examples of such articles include adhesive tapes, including double-sided and single-sided tapes; label stock; tag constructions; packaging products and assemblies, including food packaging, packaging for household goods and industrial products, and particularly reusable packaging; and other items.

[00126] Figure 6 illustrates a tape article 100 in accordance with an embodiment of the present invention. The tape article 100 is shown in roll form, however, it will be appreciated that the tape may be in a flat, sheet, or Z-fold form. The tape article 100 generally includes a substrate 110 that defines a first face 112 and a second oppositely directed face 114. The tape 100 includes a layer or region of an adhesive as described herein disposed on one or both faces 112, 114. One or more release coatings and/or low energy coatings of surface can be used as described in more detail by this document.

[00127] Figure 7 is a schematic cross-sectional view of a tape 100A comprising a substrate 110 defining a first face 112 and an oppositely directed second face 114. The tape 100A also comprises a layer or region of an adhesive 120 disposed on one of the faces, such as face 114. One or more low surface energy coatings may be disposed on face 112 of substrate 110.

[00128] Figure 8 is a schematic cross-sectional view of a tape 100B comprising a substrate 110 defining a first face 112 and an oppositely directed second face 114. The tape 100B also comprises a layer or region of an adhesive 120 disposed on one of the faces, such as face 114. Tape 100B also comprises a release liner 130 that covers adhesive 120. One or more low surface energy coatings may be disposed on face 112 of substrate 110.

[00129] Figure 9 is a schematic cross-sectional view of a tape 100C comprising a substrate 110 defining a first face 112 and an oppositely directed second face 114. The tape 100C also comprises a first layer or region of an adhesive 120 disposed on one of the faces, such as face 114. Tape 100B also comprises a second layer or region of an adhesive 125 disposed on face 112 of substrate 110.

[00130] Figure 10 is a schematic cross-sectional view of a tape 100D comprising a substrate 110 defining a first face 112 and an oppositely directed second face 114. The tape 100D also comprises a first layer or region of an adhesive 120 disposed on one of the faces, such as face 114. The tape 100D also comprises a second layer or region of an adhesive 125 on the face 112. The tape 100D also comprises a first release liner 130 which covers the adhesive 120. , the tape 100D further comprises a second release liner 135 which covers the adhesive 125.

[00131] Figure 11 is a schematic cross-sectional view of a sealing, closing or reclosing assembly 200 according to the present invention. This assembly comprises a first substrate 210 defining a first substrate face 212, a second substrate 230 defining a second substrate face 214, and one or more layers or regions of an adhesive 220 defining an adhesive face 222. The adhesive 220 is disposed on one or both faces of substrate 212, 214. Adhesive 220 serves to seal and/or adhere substrates 210, 230 together after contact between adhesive face 222 and substrate face 212. As will be understood, Adhesive 220 is one of the adhesives described herein. Set 200 can be used in association with and/or incorporated into a wide variety of packaging products, including, for example, food packaging, household appliance packaging, product packaging, industrial and, in particular, refillable packaging.

[00132] The adhesive layer can have a thickness as desired for a specific purpose or intended use. In one embodiment, the adhesive layer can have a thickness from about 10 to about 125, or from about 10 to about 75, or from about 10 to about 50 microns. In one embodiment, the coat weight of the adhesive can be in the range of about 10 to about 50 grams per square meter (g/m 2 ) and, in one embodiment, about 20 to about 35 g/m 2 .

[00133] The release coatings for use in the present invention may be those known in the art or those subsequently discovered. In general, suitable release coatings include, but are not limited to, polyethylene coated papers with a commercial silicone release coating, polyethylene terephthalate films coated with polyethylene with a commercial silicone release coating, or cast polypropylene films. which may be engraved with a pattern or patterns while making such skins and subsequently coated with a commercial silicone release coating. An exemplary release coating is kraft paper which has a low-density polyethylene coating on the front with a silicone release coating and a high-density polyethylene or polypropylene coating on the back. Other release coatings known in the art are also suitable provided they are selected for their release characteristics relative to the pressure sensitive adhesive chosen for use in the adhesive article, i.e. the adhesive will have a greater affinity for the facing material than the coating. .

[00134] As noted earlier, one or more low surface energy coatings can be used on articles using the adhesives described herein. For example, for laminated tape products, it may be desirable to provide a coating of a low surface energy agent along the back face of a substrate or tape component that contacts the adhesive. Non-limiting examples of low energy coatings include silicone agents, polypropylene or other polyolefins, certain fluorocarbons and certain fatty acid esters.

[00135] A benefit of specific adhesives of the present invention involves maintaining performance criteria upon continuous exposure to UV radiation. For example, a disadvantage of many conventional UV cured randomly crosslinked webs of adhesives is that additional UV exposure results in additional crosslinking. This in turn can result in undesirable changes to the adhesive and/or its performance. Specifically, this may be undesirable for downstream UV printed clear or transparent labels. On the other hand, in many embodiments of the present invention, the adhesives do not exhibit changes in performance with additional UV exposure.

Examples

[00136] The following test methods were used to evaluate the properties of various compositions, precursors, pre-adhesives and adhesives of the present invention.

[00137] All adhesion data were tested on polypropylene (PP) facestocks without crown treatment. Samples were isolated from solvent by solvent pouring, with controlled thicknesses of 820 grams per square meter, onto paper with a silicone release layer cured with 100% Pt solids and placed in forced air ovens at temperatures of 60- 120°C. The stickers were then transfer coated onto PP. All samples are stored in a climate-controlled room for 24 hours prior to testing.

[00138] The average molecular weight (Mw) and polydispersity (PDI) were determined by gel permeation chromatography (GPC). Samples were evaluated on a Waters Acquity Advance polymer chromatography system. The eluent used was the stabilizer containing tetrahydrofuran (THF). The measurement was carried out at 35°C. Separation was performed using HSP Gel RT MB-M (range 1,000 to 4,000,000 Dalton), HSP Gel HT MB-L/M (range 500-4,000,000 Dalton) and HSP Gel HR 1.0 (Range 500-4,000,000 Dalton) columns. range of 100-1,000 Dalton). The sample concentration was 2 g/L, the flow rate 0.7 mL/min. The measurement was carried out according to polystyrene standards.

[00139] The adhesive samples were cast from solvents and lightly dried to a solvent-free coating. The coating is then cured and heat welded onto 5 µm LS Mitex membrane filters. Filters are then soaked in THF for 1 week. Weights before and after immersion are compared. Percent gel/insoluble = w/w after immersion - w/w after immersion * 100.

[00140] Melt flow was measured on a TA Instruments AR2000 rheometer equipped with a cone and plate clamp. The experiments were carried out with a temperature variation of 100°C to 130°C. The temperature increment rate was fixed at 1°C/min and a shear rate of 0.25 sec -1.

[00141] DMA was performed on a TA Instruments AR2000 rheometer equipped with parallel plate clamps. 1.0 mm thick samples were placed in the clamp and annealed at 70oC for 10 minutes to ensure good adhesion. Samples were then cooled to -60°C to initiate a temporary sweep to 150°C at an increment rate of 3°C/min. During the temperature increment, the samples were oscillated at a frequency of 10 rad/s. 90 degree shells per Method F. PSTC 101. Chemicals used and their suppliers are listed below.

[00142] Table 1

Example 1 (precursor): Preparation of segmented acrylic polymer with epoxy functionality using SFRP agent as acrylation precursor (KH6-2)

[00143] An acrylic copolymer with reactive functionalities positioned in a segment adjacent to the end of the polymer chain is prepared as follows. Into a 1500 ml reactor equipped with a heating jacket, stirrer, reflux condenser, feed tanks and nitrogen gas inlet, 7.25 g of BlocBuilderMA (SFRP agent) is charged. The reactor is then inert with nitrogen for 1 hour at 0.5 liters/min. Monomers and solvents are added in the following amounts to a feed vessel and quenched with nitrogen for 1 hour at 0.5 liters/min. After inertia, the mixture of monomer and solvent was added to the reactor to generate the segment adjacent to the ends of the polymeric chain. 71.32g Butyl Acrylate 71.32g 2-Ethylhexyl Acrylate 141.85g Propyl Acetate

[00144] The reactor feed is heated to 70°C (reactor jacket to 81°C) to start the BlocbuilderMA reaction with the initial acrylate monomers. At 70°C, T = 0 and holding below 85°C for 30 minutes to complete the initial reaction. At this point, Blocbuilder MA has added acrylate groups and is inert until heated above 100°C. At the end of the 30 minute period, the reaction is heated under reflux conditions (reactor jacket 130°C) with a constant nitrogen purge. At 100°C, 18.90 g of glycidyl methacrylate are added to the reactor and a wait of 90 minutes is started, in which the reaction will reach a reflux during this wait at approximately 112°C. This is to create the epoxy functional segment with a theoretical Mn of 8489 g/mol. Over the period of 90 minutes, a reagent feed mixture with an active nitrogen purge of 336.79 g propyl acetate, 641.88 g 2-ethylhexyl acrylate, and 641.88 g butyl acrylate is weighed into a feed vessel and inert with nitrogen at 0.5 liters/minute. After the initial period of 90 minutes, the reagent feed is added over a period of sixty minutes to the reactor at a rate of 2 grams/minute. After sixty minutes of feeding, the rate is increased to 4.00 grams/min for 30 minutes. After the 30-minute feed rate 2, the feed rate is increased to 8.00 grams/minute until the reagent feed is depleted. During reagent feeding, the reaction temperature is maintained at 115-122°C. Reaction conditions are maintained after completion of reagent feeding until at least about 90% conversion of butyl acrylate and 2-ethylhexyl acrylate is achieved. The conversion for this example was greater than 92.0%. This is to create the remainder of the non-epoxy functional segment adjacent to the epoxy functional segment at the end of the polymer. The total theoretical Mn of the non-epoxy functional segment is 67,463 g/mol. At this point, the polymer is cooled to about 85°C. Once the polymer is at about 85°C, 1.45 g tertiary amyl peroxy pivalate and 67.36 g propyl acetate are mixed in a 100 mL feed vessel and under an inert atmosphere for 15 minutes with nitrogen at 0 .5 liters/minute. After inertia, the pivalate solution is added to the reactor for ninety minutes. On completion of the pivalate feed, the reaction temperature is held between 85°C and 90°C for 1 hour. The polymer from the resulting solution is then cooled to room temperature. During cooling, 4.39 g of sodium acetate and 24.86 g of propyl acetate were added to the reactor to neutralize the acid in the BlocbuilderMA. Once at room temperature, the polymer is discharged from the reactor. The theoretical molecular weight was 75,953 g/mol Mn with 7 epoxy groups at one end of the chain.

[00145] The polymer from the resulting solution was isolated from the solvent to form a liquid polymer using rotary evaporation and evaluated for melt viscosity using a cone and plate mounted on a dynamic mechanical analysis rheometer.

Example 2 (pre-adhesive): Preparation of segmented acrylic polymer with ENE (double bond) functionality Using example 1 as a precursor to achieve at least about 80% acrylation with acrylic acid (EB15-17)

[00146] An acrylic copolymer with ENE reactive functionalities positioned in a segment adjacent to the end of the polymer chain is prepared as follows. In a 1500ml reactor equipped with a heating jacket, stirrer, reflux condenser, feed tanks and nitrogen gas inlet, 469.31g of Example 1 (epoxy precursor) is charged). The reactor charge is heated to 70°C (reactor jacket to 79°C). Once at 70°C, 3.41g of Hycat 2000s (chromium catalyst) and 64.71g of propyl acetate are added to the reactor. The mixture is allowed to mix under agitation at 150 rpm for 10 minutes. After mixing the catalyst, 1.80 g of acrylic acid is added to the reactor along with 5.00 g of propyl acetate as a rinse for any residual acrylic acid. The mixture was kept under stirring for approximately 40 minutes. After mixing, 1.70 g of 4-Hydroxy-TEMPO and 32.30 g of propyl acetate are added to the reactor to prevent polymerization of the double bonds of the acrylated pre-adhesive composition. The mixture was kept at 70-72°C for 24 hours. Acrylic acid conversion was monitored with gas chromatography during this holding time. After 24 hours, the polymer was cooled to room temperature and discharged. The resulting polymer has 3 epoxy groups that have been converted to ENE functionality, resulting in a pre-adhesive that is UV/actinic curable.

Example 3: Preparation of segmented acrylic polymer with ENE functionality after acrylation of Example 1 and formulated for UV curing of pre-adhesive (AK4-11).

[00147] Example 1 was formulated with 1% on solids Irgacure 2959, which was purchased from BASF, and 250 ppm of 4-Hydroxy TEMPO. In addition, Example 1 was formulated with 1% in solids Hycat 2000s and sufficient molar equivalent acrylic acid to acrylate at least about 80% of the epoxy groups in Example 1. All components were mixed in an 8 oz amber bottle . using a cup. After mixing, the flask was placed in an oven at 70°C for 24 hours to complete the acrylation step.

[00148] Table 2

[00149] Table 3: Results

Example 4: Preparation of segmented acrylic polymer with acid functionality using SFRP agent as acrylation precursor (KH6-4)

[00150] An acrylic copolymer with reactive functionalities positioned in a segment adjacent to the end of the polymer chain is prepared as follows. Into a 1500 ml reactor equipped with a heating jacket, stirrer, reflux condenser, feed tanks and nitrogen gas inlet, 9.10g of MA (SFRP agent) is charged. The reactor is then inert with nitrogen for 1 hour at 0.5 liters/min. Monomers and solvents are added in the following amounts to a feed vessel and quenched with nitrogen for 1 hour at 0.5 liters/min. After inertia, the mixture of monomer and solvent was added to the reactor to generate the segment adjacent to the ends of the polymeric chain. 89.57g Butyl Acrylate 89.57g 2-Ethylhexyl Acrylate 12.04g Acrylic Acid 178.14g Propyl Acetate

[00151] The reactor charge is heated to 70°C (reactor jacket to 81°C) to start the Blocbuilder MA reaction with the initial acrylate monomers. At 70°C, T = 0 and holding below 85°C for 30 minutes to complete the initial reaction. At this point, Blocbuilder MA has added acrylate groups and is inert until heated above 100°C. At the end of the 30 minute period, the reaction is heated under reflux conditions (reactor jacket 130°C) with a constant nitrogen purge. At 100°C, a hold of 90 minutes, in which the reaction will reach a reflux during this wait at approximately 112°C. This is to create the acid functional segment with a theoretical Mn of 8.004 g/mol. Over the period of 90 minutes, a reagent feed mixture with an active nitrogen purge of 422.96g propyl acetate, 806.11g 2-ethylhexyl acrylate, and 806.11g butyl acrylate is weighed in a feeding vessel and inert with nitrogen at 0.5 liters/minute. After the initial period of 90 minutes, the reagent feed is added over a period of sixty minutes to the reactor at a rate of 2 grams/minute. After sixty minutes of feeding, the rate is increased to 4.00 grams/min for 30 minutes. After the 30-minute feed rate 2, the feed rate is increased to 8.00 grams/minute until the reagent feed is depleted. During reagent feeding, the reaction temperature is maintained at 115-122°C. Reaction conditions are maintained after completion of reagent feeding until at least about 90% conversion of butyl acrylate and 2-ethylhexyl acrylate is achieved. This is to create the remainder of the non-acid functional segment adjacent to the epoxy functional segment at the end of the polymer. The total theoretical Mn of the non-acid functional segment is 67,500 g/mol. At this point, the polymer is cooled to 85°C. Once the polymer is 85°C, 1.80g tertiary amyl peroxypivalate and 84.59g propyl acetate are mixed in a 100 mL feed vessel and under an inert atmosphere for 15 minutes with nitrogen at 0.5 liters/ minute. After inertia, the pivalate solution is added to the reactor for ninety minutes. On completion of the pivalate feed, the reaction temperature is held between 85°C and 90°C for 1 hour. The polymer from the resulting solution is then cooled to room temperature and discharged from the reactor. Theoretical molecular weight was 75,505 g/mol Mn with 7 acid groups at one end of the chain. The measured Mn was 48197 g/mol with a PDI of 2.45.

[00152] The polymer from the resulting solution was isolated from the solvent using rotary evaporation and evaluated for melt viscosity using a cone and plate mounted on a dynamic mechanical analysis rheometer.

Example 5: Preparation of segmented acrylic polymer with ENE functionality using Example 4 as a precursor to achieve at least about 80% acrylation with glycidyl methacrylate (KH6-8)

[00153] An acrylic copolymer with ENE reactive functionalities positioned in a segment adjacent to the end of the polymer chain is prepared as follows. In a 1500ml reactor equipped with a heating jacket, stirrer, reflux condenser, feed tanks and nitrogen gas inlet, 257.32g of Example 4 (acid precursor) is charged. Under stirring at 50 rpm, 0.04 g of 4-hydroxy-TEMPO and 3.96 g of methyl ethyl ketone are added to the reactor and allowed to mix for 5 minutes. Then, 2.11 g of glycylidyl methacrylate is added to the reactor and allowed to mix for 5 minutes. Finally, 1.00 g of Hycat 200S and 18.94 g of propyl acetate are added to the reactor and allowed to mix. Once the Hycat is added to the reactor, the reactor charge is heated to 70°C (reactor jacket to 83°C). Once at 70°C, T = 0 and the agitation is increased to 100 rpm. The mixture was kept at 72-74°C for 7 hours. Conversion of glycidyl methacrylate was monitored with gas chromatography during this holding time. After 7 hours, the polymer was cooled to room temperature and discharged. The resulting polymer has 4.5 acid groups that have been converted to ENE functionality, resulting in a pre-adhesive that is UV/actinic radiation curable.

Example 6: Preparation of segmented acrylic polymer with ENE functionality using Example 4 as a precursor to achieve at least about 80% acrylation with glycidyl methacrylate (KH6-9)

[00154] An acrylic copolymer with ENE reactive functionalities positioned in a segment adjacent to the end of the polymer chain is prepared as follows. In a 1500 ml reactor equipped with a heating jacket, stirrer, reflux condenser, feed tanks and nitrogen gas inlet, 289.65g of Example 4 (acid precursor) is charged. Under stirring at 75 rpm, 0.04 g of 4-hydroxy-TEMPO and 3.96 g of methyl ethyl ketone are added to the reactor and allowed to mix for 5 minutes. Then, 2.37g of glycylidyl methacrylate is added to the reactor and allowed to mix for 5 minutes. Finally, 1.12g of Hycat 200S and 21.34g of propyl acetate are added to the reactor and allowed to mix. Once the Hycat is added to the reactor, the reactor charge is heated to 80°C (reactor jacket to 84°C). Once at 80°C, T = 0 and the agitation is increased to 100 rpm. The mixture was held at 79-81°C for 7 hours. Conversion of glycidyl methacrylate was monitored with gas chromatography during this holding time. After 7 hours, the polymer was cooled to room temperature and discharged. The resulting polymer has 5 acid groups that have been converted to ENE functionality, resulting in a pre-adhesive that is curable by actinic/UV radiation.

Example 7: Preparation of segmented acrylic polymer with ENE functionality using Example 4 as a precursor to achieve 80% acrylation with glycidyl methacrylate (KH6-11)

[00155] An acrylic copolymer with ENE reactive functionalities positioned in a segment adjacent to the end of the polymer chain is prepared as follows. In a 1500ml reactor equipped with a heating jacket, stirrer, reflux condenser, feed tanks and nitrogen gas inlet, 331.43g of Example 4 (acid precursor) is charged. Under stirring at 75 rpm, 0.24 g of Hycat 200S and 4.53 g of propyl acetate are added to the reactor and allowed to mix for 5 minutes. Then, 0.05 g of 4-hydroxy-TEMPO and 0.91 g of propyl acetate are added to the reactor and allowed to mix for 5 minutes. Finally, 2.50 g of glycylidyl methacrylate is added to the reactor and allowed to mix. Once the GMA is added to the reactor, the reactor charge is heated to 80°C (reactor jacket to 84°C). Once at 80°C, T = 0 and the agitation is increased to 100 rpm. The mixture was held at 79-81°C for 2 hours. Conversion of glycidyl methacrylate was monitored with gas chromatography during this holding time. After 2 hours, the polymer was cooled to room temperature and discharged. The resulting polymer has 0.5 acid groups that have been converted to ENE functionality, resulting in a pre-adhesive that is UV/actinic radiation curable.

[00156] Table 4

Examples 8-12: Preparation of segmented acrylic polymer with ENE functionality after various levels of acrylation of Example 4 and formulated for UV curing of the pre-adhesive.

[00157] Example 4 was formulated with 1% on solids Irgacure 2959, which was purchased from BASF, and 200 ppm of 4-Hydroxy TEMPO purchased from Sigma Aldrich. In addition, Example 4 was formulated with 0.5% solid Hycat 2000s and sufficient molar equivalents of glycidyl methacrylate (GMA) to acrylate from 50% to 100% of the acid groups in Example 4. All components were mixed in a 8 oz amber bottle. using a cup. After mixing, the flask was placed in an oven at 70°C for 24 hours to complete the acrylation step.

[00158] Table 5

[00159] Table 6: Results

Examples 13-16: Preparation of segmented acrylic polymer with ENE functionality after various levels of acrylation of Example 4 and formulated for UV curing of the pre-adhesive.

[00160] Example 4 was formulated with 1% on solids Irgacure 2959, which was purchased from BASF, and 200 ppm of 4-Hydroxy TEMPO purchased from Sigma Aldrich. Performance aids Dertofen T115 (T115) purchased from DTR and dipentaerythritol hexyl acrylate (DPHA) purchased from Sigma Aldrich were formulated in Example 4 at various levels. In addition, Example 4 was formulated with 0.5% solid Hycat 2000s and sufficient molar equivalents of glycidyl methacrylate (GMA) to acrylate to 80% of the acid groups in Example 4. All components were mixed in a vial of amber 8 oz. using a cup. After mixing, the flask was placed in an oven at 70°C for 24 hours to complete the acrylation step.

[00161] Table 7

[00162] Table 8: Results

Example 17: Preparation of segmented acrylic polymer with anhydride functionality using SFRP agent as acrylation precursor (KH6-7)

[00163] An acrylic copolymer with reactive functionalities positioned in a segment adjacent to the end of the polymer chain is prepared as follows. Into a 1500 ml reactor equipped with a heating jacket, stirrer, reflux condenser, feed tanks and nitrogen gas inlet, 9.08g of MA (SFRP agent) is charged. The reactor is then inert with nitrogen for 1 hour at 0.5 liters/min. Monomers and solvents are added in the following amounts to a feed vessel and quenched with nitrogen for 1 hour at 0.5 liters/min. After inertia, the mixture of monomer and solvent was added to the reactor to generate the segment adjacent to the ends of the polymeric chain. 89.41g Butyl Acrylate 89.41g 2-Ethylhexyl Acrylate 16.36g Maleic Anhydride 177.83g Propyl Acetate

[00164] The reactor charge is heated to 70oC (reactor jacket to 81oC) to start the BlocbuilderMA reaction with the initial acrylate monomers. At 70°C, T = 0 and holding below 85°C for 30 minutes to complete the initial reaction. At this point, Blocbuilder MA has added acrylate groups and is inert until heated above 100°C. At the end of the 30 minute period, the reaction is heated under reflux conditions (reactor jacket 130°C) with a constant nitrogen purge. At 100°C, a 60-minute wait, in which the reaction will reach a reflux during this wait at approximately 112°C. This is to create the epoxy functional segment with a theoretical Mn of 8189 g/mol. Over the period of 60 minutes, a reagent feed mixture with an active nitrogen purge of 422.23g propyl acetate, 804.71g 2-ethylhexyl acrylate, and 804.71g butyl acrylate is weighed in a feeding vessel and inert with nitrogen at 0.5 liters/minute. After the initial period of 60 minutes, the reagent feed is added over a period of sixty minutes to the reactor at a rate of 2 grams/minute. After sixty minutes of feeding, the rate is increased to 4.00 grams/min for 30 minutes. After the 30-minute feed rate 2, the feed rate is increased to 8.00 grams/minute until the reagent feed is depleted. During reagent feeding, the reaction temperature is maintained at 115-122°C. Reaction conditions are maintained after completion of reagent feeding until at least 90% conversion of butyl acrylate and 2-ethylhexyl acrylate is achieved. This is to create the rest of the non-anhydride functional segment adjacent to the anhydride functional segment at the end of the polymer. The total theoretical Mn of the non-anhydride functional segment is 67,531 g/mol. At this point, the polymer is cooled to 85°C. Once the polymer is 85°C, 1.80g of tertiary amyl peroxypivalate and 84.45g of propyl acetate are mixed in a 100 mL feed vessel and under an inert atmosphere for 15 minutes with nitrogen at 0.5 liters/ minute. After inertia, the pivalate solution is added to the reactor for ninety minutes. On completion of the pivalate feed, the reaction temperature is held between 85°C and 90°C for 1 hour. The polymer from the resulting solution is then cooled to room temperature and discharged from the reactor. Theoretical molecular weight was 75,722 g/mol Mn with 7 anhydride groups at one end of the chain.

[00165] The polymer from the resulting solution was isolated from the solvent using rotary evaporation and evaluated for melt viscosity using a cone and plate mounted on a dynamic mechanical analysis rheometer.

Example 18: Preparation of segmented acrylic polymer with ENE functionality using example 17 as a precursor to achieve 100% acrylation with 4-hydroxybutyl acrylate (JRL6-143)

[00166] An acrylic copolymer with ENE reactive functionalities positioned in a segment adjacent to the end of the polymer chain is prepared as follows. Into a 1500ml reactor equipped with a heating jacket, stirrer, reflux condenser, feed tanks and nitrogen gas inlet, 545.22g of Example 17 (anhydride precursor) is charged. Under stirring at 125 rpm, 0.14 g of 4-hydroxy-TEMPO and 2.59 g of propyl acetate are added to the reactor and allowed to mix for 5 minutes. Then, 5.42 g of 4-hydroxy butyl acrylate is added to the reactor and allowed to mix for 5 minutes. This mixture was mixed overnight at room temperature. The next day, the reactor charge is heated to 80°C (reactor jacket at 85°C). Once at 80°C, T = 0 and 0.41 g of methanesulfonic acid and 3.70 g of ethyl acetate are added to the reactor. The mixture was kept at 78-82°C for 24 hours. Conversion of 4-hydroxy-butyl acrylate was monitored with gas chromatography during this holding time. After 24 hours, the polymer was cooled to room temperature and discharged. The resulting polymer has 7 maleic anhydride groups that have been converted to ENE functionality, resulting in a pre-adhesive that is UV/actinic radiation curable.

Example 19: Pilot scale preparation of segmented acrylic polymer with ENE functionality using SFRP agent (PP85-65)

[00167] An acrylic copolymer with ENE reactive functionalities positioned in a segment adjacent to the end of the polymer chain is prepared as follows. In a 100 gallon reactor equipped with a heating jacket, stirrer, reflux condenser, feed tanks and nitrogen gas inlet, 1.53 pounds of BlocBuilder MA (SFRP agent) is charged. The reactor is then inert with nitrogen for 1 hour at 0.5 liters/min. Monomers and solvents are added in the following amounts to a feed vessel and quenched with nitrogen for 1 hour at 0.5 liters/min. After inertia, the mixture of monomer and solvent was added to the reactor to generate the segment adjacent to the ends of the polymeric chain. 15.1 lbs Butyl Acrylate 15.1 lbs 2-Ethylhexyl Acrylate 3.90 lbs Maleic Anhydride 27.5 lbs Propyl Acetate

[00168] The reactor charge is heated to 70°C (reactor jacket to 80°C) to start the BlocbuilderMA reaction with the starting acrylate monomers. At 70°C, T = 0 and holding below 85°C for 30 minutes to complete the initial reaction. At this point, Blocbuilder MA has added acrylate groups and is inert until heated above 100°C. At the end of the 30 minute period, the reaction is heated under reflux conditions (reactor jacket 130°C) with a constant nitrogen purge. At 100°C, T = 0 and a hold is initiated, in which the reaction will reach a reflux during this hold at approximately 114°C. This is to create the anhydride functional segment with a theoretical Mn of 8492 g/mol. During the hold, a reagent feed mixture with an active nitrogen purge of 47.9 pounds of propyl acetate, 135.8 pounds of 2-ethylhexyl acrylate, and 135.8 pounds of butyl acrylate is weighed in a feeding container. After the initial monomer conversion is >60% converted, the reagent feed is added to the reactor over a period of sixty minutes through a nitrogen sparger (0.5 L/min) at a rate of 0.95 pounds/minute . After the sixty minute feed, the rate is increased to 1.18 lbs/min for 60 minutes. After Feed Rate 2 of 60 minutes, the Feed Rate is increased to 1.28 lbs/minute until reagent feed is exhausted (~150 minutes). During reagent feeding, the reaction temperature is maintained at 115-122°C. Reaction conditions are maintained after completion of reagent feeding until at least 90% conversion of butyl acrylate and 2-ethylhexyl acrylate is achieved. This is to create the rest of the non-anhydride functional segment adjacent to the anhydride functional segment at the end of the polymer. The total theoretical Mn of the non-anhydride functional segment is 67,633 g/mol. At this point, the polymer is cooled to 85°C. Once the polymer is 85°C, 0.30 pounds of tertiary amyl peroxy pivalate and 13.4 lbs of propyl acetate are placed in a feed vessel and added to the reactor over thirty minutes. At the conclusion of the pivalate feed, the reaction temperature is maintained between 85°C and 90°C for 2 hours.

[00169] After waiting 2 hours, the nitrogen purge is turned off and 0.0769 pounds of 4-hydroxy-TEMPO, 5.7 pounds of 4-hydroxy butyl acrylate are mixed until homogeneous. Once mixed, the TEMPO and HBA mixture is added to the reactor and allowed to mix under agitation for 5 minutes. Once mixed, 0.308 pounds of methanesulfonic acid is added to the reactor along with 1.7 pounds of propyl acetate rinse. The reaction is held at 85°C until greater than 80% of the HBA is converted. Conversion is monitored by gas chromatography. When HBA conversion is above 80%, an additional 0.154 pounds of 4-hydroxy TEMPO and 19.2 pounds of n,n-dimethyltetradecylamine (ADMA 14) are added to the reactor. Finally, 2.50 pounds of Esacure one is dissolved in 25.00 pounds of propyl acetate and added to the reactor and allowed to mix. The polymer from the resulting solution is then isolated via pot extraction and discharged from the reactor. Theoretical molecular weight was 76,125 g/mol Mn with 10 anhydride groups at one end of the chain which were converted to ENE functionality to result in an actinic/UV radiation curable pre-adhesive.

Example 20: Formulation of Example 19 - Pilot Scale Preparation of Segmented Acrylic Polymer with ENE Functionality Using 7.5 Parts Per Hundred Adhesive SFRP Agent (AK6-33)

[00170] The terpene phenolic resin adhesive used was Dertophene T115 acquired from DRT.

[00171] Table 9, Performance

Example 21: Preparation of segmented acrylic polymer with alcohol functionality using SFRP agent as precursor of (KH5-39) acrylation (KH7-31)

[00172] An acrylic copolymer with reactive alcohol functionalities positioned in a segment adjacent to the end of the polymer chain is prepared as follows. Into a 1500 ml reactor equipped with a heating jacket, stirrer, reflux condenser, feed tanks and nitrogen gas inlet, 10.55 g of MA (SFRP agent) is charged. The reactor is then inert with nitrogen for 1 hour at 0.5 liters/min. Monomers and solvents are added in the following amounts to a feed vessel and quenched with nitrogen for 1 hour at 0.5 liters/min. After inertia, the mixture of monomer and solvent was added to the reactor to generate the segment adjacent to the ends of the polymeric chain. 99.73g butyl acrylate 38.78g butyl acrylate 7.98g 4-hydroxybutyl acrylate 150.00g propyl acetate

[00173] The reactor charge is heated to 70°C (reactor jacket to 81°C) to start the BlocbuilderMA reaction with the initial acrylate monomers. At 70°C, T = 0 and holding below 85°C for 30 minutes to complete the initial reaction. At this point, Blocbuilder MA has added acrylate groups and is inert until heated above 100°C. At the end of the 30 minute period, the reaction is heated under reflux conditions (reactor jacket 130°C) with a constant nitrogen purge. At 100°C, a 60-minute wait, in which the reaction will reach a reflux during this wait at approximately 112°C. This is to create the alcohol functional segment with a theoretical Mn of 5290 g/mol. During the 60 minute hold period, a reagent feed mixture with an active nitrogen purge of 250.00 g propyl acetate, 349.05 g methyl acrylate, and 897.55 g butyl acrylate is weighed out into a feed vessel and made inert with nitrogen at 0.5 liters/minute. After the initial period of 60 minutes, the reagent feed is added over a period of sixty minutes to the reactor at a rate of 2 grams/minute. After sixty minutes of feeding, the rate is increased to 4.00 grams/min for 30 minutes. After the 30-minute feed rate 2, the feed rate is increased to 8.00 grams/minute until the reagent feed is depleted. During reagent feeding, the reaction temperature is maintained at 115-122°C. Reaction conditions are maintained after completion of reagent feeding until residual monomer is less than 1%. This is to create the remainder of the non-alcohol functional segment adjacent to the alcohol functional segment at the end of the polymer. The total theoretical Mn of the non-alcohol functional segment is 45,019 g/mol. The polymer from the resulting solution is then cooled to room temperature and discharged from the reactor. The theoretical molecular weight was 50,309 g/mol Mn with 2 alcohol groups at one end of the chain.

Examples 22-26- Formulations of Example 21 with Diisocyano Acrylate D-200 and Preparation of Segmented Acrylic with ENE Functionality Using SFRP Agent (AK3-27)

[00174] Example 21 was formulated with D200 supplied by Allnex in various molar ratios of isocyanate groups to alcohol and dibutyltin dilaurate (DBTDL) supplied by Sigma Aldrich.

[00175] Table 10

[00176] Table 11: Results

Examples 27-31 - Formulations of examples 22-26 with Irgacure 4265 photoinitiator for UV curing of pre-adhesives (AK3-39)

[00177] Examples 22-26 were formulated with Irgacure 4265 supplied by BASF at 1% in dry resin for curing studies.

[00178] Table 12

[00179] Table 13, Results

Example 32: Preparation of segmented acrylic polymer with alcohol functionality using SFRP agent as acrylation precursor (KH7-31)

[00180] An acrylic copolymer with alcohol reactive functionalities positioned in a segment adjacent to the end of the polymer chain is prepared as follows. Into a 1500 ml reactor equipped with a heating jacket, stirrer, reflux condenser, feed tanks and nitrogen gas inlet, 4.66g of MA (SFRP agent) is charged. The reactor is then inert with nitrogen for 1 hour at 0.5 liters/min. Monomers and solvents are added in the following amounts to a feed vessel and quenched with nitrogen for 1 hour at 0.5 liters/min. After inertia, the mixture of monomer and solvent was added to the reactor to generate the segment adjacent to the ends of the polymeric chain.61.13g of butyl acrylate 61.16g of 2-ethylhexyl acrylate 3.52g of 4-ethyl acrylate -hydroxybutyl 121.58g propyl acetate

[00181] The reactor charge is heated to 70°C (reactor jacket to 81°C) to start the BlocbuilderMA reaction with the starting acrylate monomers. At 70°C, T = 0 and holding below 85°C for 30 minutes to complete the initial reaction. At this point, Blocbuilder MA has added acrylate groups and is inert until heated above 100°C. At the end of the 30 minute period, the reaction is heated under reflux conditions (reactor jacket 130°C) with a constant nitrogen purge. At 100°C, a 75 minute hold, in which the reaction will reach a reflux during this hold at approximately 112°C. This is to create the alcohol functional segment with a theoretical Mn of 10.283 g/mol. Over the period of 75 minutes, a reagent feed mixture with an active nitrogen purge of 288.67g propyl acetate, 550.17g 2-ethylhexyl acrylate, and 550.17g butyl acrylate is weighed in a feeding vessel and inert with nitrogen at 0.5 liters/minute. After the initial period of 75 minutes, the reagent feed is added over a period of sixty minutes to the reactor at a rate of 2 grams/minute. After sixty minutes of feeding, the rate is increased to 6.00 grams/min for 30 minutes. After the 30-minute feed rate 2, the feed rate is increased to 9.00 grams/minute until the reagent feed is depleted. During reagent feeding, the reaction temperature is maintained at 115-122°C. Reaction conditions are maintained after completion of reagent feeding until at least 90% conversion of butyl acrylate and 2-ethylhexyl acrylate is achieved. This is to create the remainder of the non-alcohol functional segment adjacent to the alcohol functional segment at the end of the polymer. The total theoretical Mn of the non-alcohol functional segment is 89,963 g/mol. At this point, the polymer is cooled to 85°C. Once the polymer is 85°C, 2.46g of tertiary amyl peroxypivalate and 118.54g of propyl acetate are mixed in a 100 mL feed vessel and under an inert atmosphere for 15 minutes with nitrogen at 0.5 liters/ minute. After inertia, the pivalate solution is added to the reactor for thirty minutes. At the conclusion of the pivalate feed, the reaction temperature is maintained between 85°C and 90°C for at least 2 hours. The polymer from the resulting solution is then cooled to room temperature and discharged from the reactor. The theoretical molecular weight was 100,247 g/mol Mn with 2 alcohol groups at one end of the chain.

Examples 33-35- Formulations of example 32 with diisocyano acrylate D-200XP and Preparation of multifunctional acrylates of segmented acrylic preadhesive with ENE functionality using SFRP agent (AK7-35)

[00182] The multifunctional acrylate used was Pentaerythritol Tetra Acrylate (PETTA) purchased from Sigma Aldrich.

[00183] D-200XP was supplied by Allnex and added to each mixture in an NCO/OH ratio of 1 to 4.

[00184] Dibutyltin dilaurate (DBTDL) was purchased from Sigma Aldrich.

[00185] 4-Hydroxy-TEMPO was purchased from Sigma Aldrich.

[00186] Esacure One was purchased from IGM Resins.

[00187] Table 14

[00188] Table 15, Results

[00189] Undoubtedly, many other benefits will become apparent with the future application and development of this technology.

[00190] Other examples consistent with the present teachings are presented in the following clauses.

[00191] Clause 1. A composition comprising a precursor and a reacting agent, the precursor comprising at least one acrylic block copolymer, the at least one acrylic block copolymer comprising, a first reactive segment of controlled molecular weight and position that comprises at least one monomer having a functional group selected from the group consisting of a self-reactive functional group, a reactive functional group, a non-reactive functional group and combinations thereof; and, a second molecular weight and position controlled segment that includes at least one monomer having a functional group selected from the group consisting of a reactive functional group, a non-reactive functional group, and combinations thereof; wherein at least one of the functional groups of the at least one acrylic block copolymer can undergo a post-polymerization functionalization reaction with the reacting agent to make the at least one acrylic block copolymer crosslinkable upon exposure to actinic radiation, wherein at least one acrylic block copolymer does not contain ethyl unsaturation

[00192] Clause 2. The composition according to clause 1, wherein the at least one acrylic block copolymer is not crosslinkable after exposure to actinic radiation.

[00193] Clause 3. The composition according to any one of clauses 1 or 2, wherein the reacting agent comprises at least one of a double bond and a functional group, the functional group being capable of reacting with at least one from among the functional group of the at least one acrylic block copolymer.

[00194] Clause 4. The composition according to any one of clauses 1 to 3, wherein the post-polymerization functionalization reaction is an acrylation reaction.

[00195] Clause 5. The composition according to any one of clauses 1 to 4, wherein the post-polymerization functionalization reaction produces an ethylically unsaturated bond in the at least one acrylic block copolymer.

[00196] Clause 6. The composition according to clause 5, wherein the ethyl unsaturated bond is a double bond.

[00197] Clause 7. The composition according to any one of clauses 1 to 6, wherein the precursor forms a pre-adhesive composition after the post-polymerization functionalization reaction of the at least one acrylic block copolymer.

[00198] Clause 8. The composition according to clause 7, wherein the pre-adhesive is at least partially cross-linkable upon exposure to actinic radiation to form an adhesive.

[00199] Clause 9. The composition according to any one of clauses 1 to 8, wherein the adhesive is a pressure sensitive adhesive.

[00200] Clause 10. The composition according to any one of clauses 1 to 9, wherein the actinic radiation is at least UV radiation and electron beam radiation.

[00201] Clause 11. The composition according to any one of clauses 1 to 10, wherein the composition is free of solvents.

[00202] Clause 12. The composition according to any one of clauses 1 to 11, wherein at least one of the precursors and pre-adhesives exhibits a viscosity within a range from about 1,000 cps (1Pa.s) at about 80,000 cps (80Pa.s) at a temperature within the range of about 110°C to about 180°C.

[00203] Clause 13. The composition according to any one of clauses 1 to 11, wherein at least one of the precursors and pre-adhesives exhibits a viscosity within a range from about 30,000 cps (30Pa.s) at about 40,000 cps (40Pa.s) at a temperature within the range of about 120°C to about 140°C.

[00204] Clause 14. The composition according to any one of clauses 1 to 11, wherein at least one of the precursors and pre-adhesives exhibits a viscosity within a range from about 40,000 cps (40Pa.s) at about 50,000 cps (50Pa.s) at a temperature within the range of about 120°C to about 140°C.

[00205] Clause 15. The composition according to any one of clauses 1 to 11, wherein at least one of the precursors and pre-adhesives exhibits a viscosity within a range from about 1,000 cps (1Pa.s) at about 15,000 cps (15Pa.s) at a temperature within the range of about 110°C to about 130°C.

[00206] Clause 16. The composition according to any one of clauses 1-15, wherein the pre-adhesive prior to activation is solvent-free and exhibits less than about 7.5% gel.

[00207] Clause 17. The composition according to any one of clauses 1 to 16, wherein the pre-adhesive before activation exhibits less than about 7.5% gel to about 99% or more solids.

[00208] Clause 18. The composition according to any one of clauses 1 to 16, wherein the pre-adhesive before activation exhibits less than about 7.5% gel at 100% solids.

[00209] Clause 19. The composition according to any one of clauses 1 to 18, wherein the first reactive segment comprises at least one monomer with a non-reactive functional group and at least one polymerizable comonomer with a cross-linkable functionality, the functionality crosslinkable comprising a self-reactive functional group and a reactive functional group.

[00210] Clause 20. The composition according to any one of clauses 1-18, wherein the first reactive segment comprises at least one monomer with a non-reactive functional group and at least one polymerizable comonomer with a cross-linkable functionality, the functionality crosslinkable comprising a self-reactive functional group.

[00211] Clause 21. The composition according to any one of clauses 1-18, wherein the first reactive segment comprises at least one monomer with a non-reactive functional group and at least one polymerizable comonomer with a cross-linkable functionality, the functionality crosslinkable comprising a self-reactive functional group.

[00212] Clause 22 The composition according to any one of clauses 1 to 21, wherein the second segment comprises at least one monomer with a non-reactive functional group and at least one monomer with a reactive functional group.

[00213] Clause 23. The composition according to any one of clauses 1 to 21, wherein the second segment includes at least one monomer having a non-reactive functional group.

[00214] Clause 24. The composition, according to any of the at least one monomer having one of the first reactive segment is the same type as the monomer having a non-reactive functional group present in the second segment.

[00215] Clause 25. The composition according to any one of clauses 1 to 24, wherein the at least one monomer having a reactive functional group within the first reactive segment is the same type as the monomer having a reactive functional group present in the second segment.

[00216] Clause 26. The composition according to any one of clauses 1 to 13, wherein the functional group of the at least one acrylic block copolymer undergoing the post-polymerization reaction is a different type of functional group than the functional group of the reaction agent.

[00217] Clause 27. The composition according to any one of clauses 1 to 13, in which the functional group of at least one acrylic block copolymer undergoing the post-polymerization reaction is the same type of functional group as the group functional reaction agent.

[00218] Clause 28. The composition, according to any one of clauses 1 to 27, in which the at least one monomer with a reactive functional group includes at least one functionalized monomer derived from Formula (I): Wherein R3 is H or CH3 and R4 is X, wherein X comprises a functional group capable of cross-linking, wherein the functional group includes at least one functional group selected from the group consisting of hydroxyl, carboxyl, carbonyl, carbonate, isocyanate, epoxy, vinyl groups, amine, amide, imide, anhydride, thiol, acid, acrylamide, acetoacetyl, alkoxymethylol, cyclic ether groups and combinations thereof.

[00219] Clause 29. The composition, according to any one of clauses 1 to 28, in which the at least one monomer with a non-reactive functional group includes at least one functionalized monomer derived from Formula (I): wherein R3 is H or CH3 and R4 is a straight or branched chain, saturated alkyl group having from 4 to 14 carbon atoms.

[00220] Clause 30. The composition according to any one of clauses 1 to 29, wherein the at least one monomer having a non-reactive functional group is derived from C1 to about C20 alkyl, aryl, or cyclic acrylates or C1 to about C20 alkyl, aryl or cyclic methacrylates.

[00221] Clause 31. The composition according to any one of clauses 1 to 30, wherein the first reactive segment comprises about 40% to about 99% by weight of the at least one monomer having a non-reactive functional group.

[00222] Clause 32. The composition according to any one of clauses 1 to 31, wherein the at least one monomer having a non-reactive functional group is non-reactive with at least one of the self-reactive functional group and the functional group reactive.

[00223] Clause 33. The composition according to any one of clauses 1-32, wherein the self-reactive functional group is selected from a group consisting of silyl, silane, anhydride, epoxy, alkoxymethylol, cyclic ethers, acetoacetyl, isocyanate, cyclic esters and thiol groups.

[00224] Clause 34. The composition, according to any one of clauses 1 to 33, in which the reactive functional group are selected from the group consisting of hydroxyl, carboxyl, carbonyl, carbonate ester, isocyanate, epoxy, vinyl, amine, amide, imide, anhydride, thiol, acid, acrylamide, acetoacetyl alkoxymethylol groups, cyclic ether groups and combinations thereof.

[00225] Clause 35. The composition, according to any one of clauses 1 to 34, in which the functional group of the reacting agent is selected from the group consisting of hydroxyl, carboxyl, carbonyl, carbonate ester, isocyanate, epoxy groups , vinyl, amine, amide, imide, anhydride, thiol, acid, acrylamide, acetoacetyl alkoxymethylol groups, cyclic ether groups and combinations thereof.

[00226] Clause 36. The composition according to any one of clauses 1 to 35, wherein the precursor has a polydispersity greater than 3.0.

[00227] Clause 37. The composition according to any one of clauses 1 to 36, wherein at least one of the precursor and pre-adhesive compositions has a number average molecular weight (Mn) within a range of about 5,000 g/mol to about 300,000 g/mol

[00228] Clause 38. The composition according to any one of clauses 1 to 37, wherein the at least one acrylic block copolymer comprises two first reactive segments A and a second segment B.

[00229] Clause 39. The composition according to clause 38, wherein the A segments are positioned on either side of the middle segment B in the polymer chain to define an ABA structure.

[00230] Clause 40. The composition according to any one of clauses 1 to 37, wherein the at least one acrylic block copolymer comprises two second segments B and a first reactive segment A.

[00231] Clause 41. The composition according to clause 40, in which the B segments are positioned on either side of the middle segment A in the polymer chain to define an ABA structure.

[00232] Clause 42. The composition, according to any one of clauses 1 to 41, in which the first reactive segment and the second segment are molecularly miscible before curing or before crosslinking, as expressed by their properties in the raw state that are indicative of a single-phase polymer.

[00233] Clause 43. The composition, according to any one of clauses 1 to 42, in which at least one of the precursor and pre-adhesive compositions is a homogeneous polymer (single phase) at a temperature range of 15 °C to 200°C.

[00234] Clause 44. The composition, according to any one of clauses 1 to 42, in which at least one of the precursor and pre-adhesive compositions is a homogeneous liquid polymer (single phase) at a temperature range of 15°C at 200°C.

[00235] Clause 45. The composition according to any one of clauses 1 to 44, wherein the composition further includes at least one component selected from the group consisting of pigments, adhesives, plasticizers, fillers, diluents, inhibitors, sensitizers, crosslinking agents, initiators, actinic radiation initiators, catalysts, antioxidants, pH controllers, drugs, bactericides, growth factors, wound healing components, deodorants, perfumes, antimicrobials, fungicides, cutting agents, flame retardants and combinations thereof.

[00236] Clause 46. The composition according to any one of clauses 1 to 45, wherein the composition further includes a multifunctional (meth)acrylate.

[00237] Clause 47. The composition, according to any one of clauses 8 and 9, in which the adhesive exhibits a modulus of elasticity/storage (G') less than the Dahlquist criterion value of 3x106 dynes/cm2 (3x105 Pa) at room temperature as determined by dynamic mechanical analysis.

[00238] Clause 48. The composition, according to any one of clauses 8 and 9, in which the adhesive exhibits a plateau shear modulus at 25oC and 1 radian per second that is between 1x105 and 6x106 dynes/cm2, as determined by dynamic mechanical analysis.

[00239] Clause 49. The composition according to any one of clauses 8, 9, 47 and 48, wherein the glass transition temperature (Tg) of the adhesive composition is within a range of about 15°C to about -115°C.

[00240] Clause 50. The composition according to any one of clauses 1 to 24, wherein the glass transition temperature (Tg) of the precursor is within a range of about 15°C to about -115°C .

[00241] Clause 51. A composition comprising the precursor according to clauses 1 to 50, a monomer having an acrylating functional group in which at least one of the functional groups of the at least one acrylic block copolymer can undergo a functionalization reaction postpolymerization with the acrylating functional group to render the at least one acrylic block copolymer crosslinkable upon exposure to actinic radiation.

[00242] Clause 52. A method of forming a curable pre-adhesive composition upon exposure to actinic radiation, the method comprising providing the precursor according to any one of clauses 1 to 50, modifying at least a portion of the functional groups of at least an acrylic block copolymer to form the pre-adhesive composition, wherein the modification produces ethylically unsaturated bonds in the at least one acrylic copolymer which, upon exposure to actinic radiation, cures the pre-adhesive composition to thereby produce an adhesive composition.

[00243] Clause 53. The method according to clause 52, wherein the adhesive is a pressure sensitive adhesive.

[00244] Clause 54. An adhesive composition produced in accordance with the method defined in accordance with clause 52.

[00245] Clause 55. The adhesive composition according to clause 54, wherein the adhesive is a pressure sensitive adhesive.

[00246] Clause 56. A method for forming an adhesive composition comprising providing a pre-adhesive composition comprising the defined precursor according to any one of clauses 1 to 50, wherein at least a portion of the functional groups of the adhesive composition pre-adhesive includes ethyl-unsaturated bonds, exposing the pre-adhesive composition to actinic radiation to thereby at least partially cure the pre-adhesive composition and form the adhesive composition.

[00247] Clause 57. The method according to clause 56, characterized in that the ethyl unsaturated bonds are produced by modifying at least a portion of the functional groups of the at least one acrylic block copolymer.

[00248] Clause 58. The method according to clause 56 or 57, wherein the adhesive is a pressure sensitive adhesive.

[00249] Clause 59. A composition consisting of the defined precursor according to any one of clauses 1 to 50; a reaction agent, a photoinitiator and, optionally, a catalyst, wherein at least one of the functional groups of the at least one acrylic block copolymer can undergo a post-polymerization functionalization reaction with the reaction agent to make the at least one an acrylic block copolymer crosslinkable after exposure to actinic radiation, wherein the at least one acrylic block copolymer does not contain ethyl unsaturation.

[00250] Clause 60 The composition according to clause 59, wherein the reaction agent comprises at least one of a double bond and a functional group, the functional group being capable of reacting with at least one of the functional group of the at least one acrylic block copolymer.

[00251] Clause 61 The composition according to clause 1 60, wherein the functional group of the reacting agent is selected from the group consisting of hydroxyl, carboxyl, carbonyl, carbonate ester, isocyanate, epoxy, vinyl, amine, amide, imide, anhydride, thiol, acid, acrylamide, acetoacetyl alkoxymethylol groups, cyclic ether groups and combinations thereof.

[00252] Clause 62 The composition according to any one of clauses 59 to 61, wherein the functional group of the at least one acrylic block copolymer undergoing the post-polymerization reaction is a different type of functional group from the functional group of the reaction agent.

[00253] Clause 63. The composition according to any one of clauses 59 to 61, wherein the functional group of at least one acrylic block copolymer undergoing the post-polymerization reaction is the same type of functional group as the group functional reaction agent.

[00254] Clause 64. A pre-adhesive comprising the precursor defined according to any one of clauses 1 to 29, which comprises post-polymerisation functionalized at least one acrylic block copolymer.

[00255] Clause 65. Pressure-sensitive adhesive, characterized in that it comprises at least one partially cross-linked pre-adhesive, defined in accordance with clause 64.

[00256] All patents, patent applications, standards and articles mentioned in this document are incorporated by reference in their entirety.

[00257] This subject includes all operable combinations of features and aspects described herein. Thus, for example, if a feature is described in association with one embodiment and another feature is described in association with another embodiment, it will be understood that the present invention includes embodiments with a combination of these features.

[00258] As described by this document, this subject solves many problems associated with previous strategies, systems and/or devices. However, it will be appreciated that various changes in details, materials and component arrangements, which have been described and illustrated herein to explain the nature of the present invention, can be made by those skilled in the art, without departing from the principle and scope of the subject matter. claimed, as expressed in the appended claims.

Claims (15)

1. Composition comprising: a precursor and a reacting agent, the precursor comprising at least one acrylic block copolymer, the at least one acrylic block copolymer comprising a first reactive segment of controlled molecular weight and position comprising at least one monomer with a functional group selected from the group consisting of a self-reactive functional group, a reactive functional group, a non-reactive functional group and combinations thereof; and a second molecular weight and position controlled segment that includes at least one monomer having a functional group selected from the group consisting of a reactive functional group, a non-reactive functional group and combinations thereof; characterized in that at least one of the functional groups of the at least one acrylic block copolymer can undergo a post-polymerization functionalization reaction with the reaction agent to make the at least one acrylic block copolymer crosslinkable after exposure to actinic radiation, wherein the at least one acrylic block copolymer does not contain ethyl unsaturation wherein the self-reactive functional group is selected from the group consisting of silyl, silane, anhydride, epoxy, alkoxymethylol, cyclic ethers, acetoacetyl groups, isocyanate, esters cyclic and thiol and wherein at least one monomer having a non-reactive functional group is derived from C1 to C20 alkyl, aryl or cyclic acrylates or C1 to C20 alkyl, aryl or cyclic methacrylates. 2. Composition, according to claim 1, characterized by the fact that one or more of the following statements (A) and (B) apply: (A) the at least one acrylic block copolymer is not crosslinkable after exposure to actinic radiation.; (B) the reacting agent comprises at least one of a double bond and a functional group, the functional group being capable of reacting with at least one of the functional groups of the at least one acrylic block copolymer. 3. Composition, according to claim 1 or 2, characterized by the fact that one or more of the following statements (A) to (C) apply: (A) the post-polymerization functionalization reaction is an acrylation reaction; (B) the post-polymerization functionalization reaction produces an ethyl-unsaturated bond in the at least one acrylic block copolymer; (C) the ethyl unsaturated bond is a double bond. 4. Composition according to any one of claims 1 to 3, characterized in that one or more of the following statements (A) to (C) apply: (A) the precursor forms a pre-adhesive composition after post-polymerization functionalization reaction of the at least one acrylic block copolymer; (B) the pre-adhesive is at least partially crosslinkable upon exposure to actinic radiation to form an adhesive, optionally the glass transition temperature (Tg) of the adhesive composition is within a range of 15°C to -115°C; wherein the glass transition temperature is determined according to the method mentioned in the specification, (C) the adhesive is a pressure sensitive adhesive, optionally the glass transition temperature (Tg) of the adhesive composition is within a range of 15°C to -115°C, where the glass transition temperature is determined according to the method mentioned in the descriptive report, 5. Composition according to any one of claims 1 to 4, characterized in that one or more of the following statements (A) to (E) apply: (A) actinic radiation is at least one UV radiation and electron beam radiation, (B) the composition is free of solvents, (C) at least one of the precursors and pre-adhesives exhibits a viscosity within a range from 1,000 cps (1Pa.s) to about 80,000 cps (80 Pa.s) at a temperature within a range of about 110°C to about 180°C, where the viscosity is determined according to the method mentioned in the specification, (D) the pre-adhesive before of activation exhibits less than about 7.5% gel to about 99% or greater solids, (E) the functional group of the at least one acrylic block copolymer undergoing the postpolymerization reaction is a different type of group functional group of the reacting agent functional group, or the functional group of at least one acrylic block copolymer undergoing the post-polymerization reaction is the same type of functional group as the reacting agent functional group. 6. Composition, according to any one of claims 1 to 5, characterized by the fact that one or more of the following statements (A) to (C) apply: (A) the first reactive segment comprises from 40% to 99 % by weight of the at least one monomer having a non-reactive functional group, (B) the reactive functional group is selected from the group consisting of hydroxyl, carboxyl, carbonyl, carbonate ester, isocyanate, epoxy, vinyl, amine, amide, imide, anhydride, thiol, acid, acrylamide, acetoacetyl alkoxymethylol groups, cyclic ether groups and combinations thereof, (C) the functional group of the reacting agent is selected from the group consisting of hydroxyl, carboxyl, carbonyl, ester groups of carbonate, isocyanate, epoxy, vinyl, amine, amide, imide, anhydride, thiol, acid, acrylamide, acetoacetyl alkoxymethylol groups, cyclic ether groups and combinations thereof. 7. Composition according to any one of claims 1 to 6, characterized in that one or more of the following statements (A) to (D) apply: (A) the first reactive segment and the second segment are molecularly miscible before curing or before crosslinking, as expressed by their properties in the raw state that are indicative of a single-phase polymer, (B) at least one of the precursor and pre-adhesive composition is a homogeneous (single-phase) polymer at a temperature range of 15°C to 200°C, (C) the composition further includes at least one component selected from the group consisting of pigments, adhesives, plasticizers, fillers, diluents, inhibitors, sensitizers, crosslinking agents , initiators, actinic radiation initiators, catalysts, antioxidants, pH controllers, drugs, bactericides, growth factors, wound healing components, deodorants, perfumes, antimicrobials, fungicides, cutting agents, flame retardants and combinations thereof , (D) the glass transition temperature (Tg) of the precursor is within a range of about 15°C to about -115°C, where the glass transition temperature is determined according to the method mentioned in the report descriptive. 8. Method for forming a curable pre-adhesive composition upon exposure to actinic radiation, the method characterized in that it comprises: providing the precursor defined in claims 1 to 7; modifying at least a portion of the functional groups of the at least one acrylic block copolymer to form the pre-adhesive composition, wherein the modification produces ethyl unsaturated linkages in the at least one acrylic copolymer which, upon exposure to actinic radiation, affects healing of the pre-adhesive composition to thereby produce an adhesive composition. 9. Method according to claim 8, characterized in that the adhesive is a pressure sensitive adhesive. 10. Adhesive composition characterized by the fact that it is produced according to the method defined in claim 8, optionally, in which the adhesive is a pressure sensitive adhesive. 11. Method for forming an adhesive composition, characterized in that it comprises: providing a pre-adhesive composition comprising the precursor defined in claims 1 to 7, wherein at least a portion of the functional groups of the pre-adhesive composition includes bonds ethyl unsaturated; exposing the pre-adhesive composition to actinic radiation to thereby at least partially cure the pre-adhesive composition and form the adhesive composition. 12. Method, according to claim 11, characterized in that one or more of the following statements (A) and (B) applies: (A) ethylically unsaturated bonds are produced by modifying at least a portion of the functional groups of the at least one acrylic block copolymer, (B) the adhesive is a pressure sensitive adhesive. 13. Composition characterized by the fact that it consists of: the precursor defined in claims 1 to 7; a reaction agent, a photoinitiator and, optionally, a catalyst wherein at least one of the functional groups of the at least one acrylic block copolymer can undergo a post-polymerization functionalization reaction with the reaction agent to make the at least one crosslinkable acrylic block copolymer upon exposure to actinic radiation, wherein the at least one acrylic block copolymer does not contain ethyl unsaturation. 14. Pre-adhesive characterized in that it comprises the precursor defined in claims 1 to 7, which comprises post-polymerization functionalized at least one acrylic block copolymer. 15. Pressure-sensitive adhesive, characterized in that it comprises at least one partially cross-linked pre-adhesive, defined in claim 14.